Compositions comprising estolide compounds and methods of making and using the same

ABSTRACT

Provided herein are compositions comprising at least one estolide compound of formula: 
                         
in which n is an integer equal to or greater than 0; m is an integer equal to or greater than 1; R 1 , independently for each occurrence, is selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; R 2  is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; and R 3  and R 4 , independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched. Also provided are uses of the compositions described herein.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Patent Application No. 61/498,499, filed Jun. 17, 2011, andU.S. Provisional Patent Application No. 61/569,046, filed Dec. 9, 2011,which are incorporated herein by reference in their entireties for allpurposes.

FIELD

The present disclosure relates to compositions comprising estolidecompounds and methods of making the same, such as hydraulic fluids,4-stroke lubricants, food-grade lubricants, refrigerating fluids,compressor fluids, metalworking fluids, and plasticized compositions.

BACKGROUND

Lubricant compositions typically comprise a base oil, such as ahydrocarbon base oil, and one or more additives. Exemplary lubricantcompositions may include hydraulic fluids, 4-stroke lubricants,food-grade lubricants, refrigerating fluids, compressor fluids, andmetalworking fluids. Plastics and plasticized compositions typicallycomprise a polymeric material and a plasticizer.

SUMMARY

Described herein are compositions comprising at least one estolidecompound, and methods of making and using the same.

In certain embodiments, the composition comprises at least one estolidecompound of Formula I:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, and 12;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;

wherein each fatty acid chain residue of said at least one compound isindependently optionally substituted.

In certain embodiments, the composition comprises at least one estolidecompound of Formula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched.

In certain embodiments, the composition comprises at least one estolidecompound of Formula III:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is an integer equal to or greater than 0;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted.

DETAILED DESCRIPTION

The use of lubricants and lubricant-containing compositions may resultin the dispersion of such fluids, compounds, and/or compositions in theenvironment. Petroleum base oils used in common lubricant compositions,as well as additives, are typically non-biodegradable and can be toxic.The present disclosure provides for the preparation and use ofcompositions comprising partially or fully bio-degradable base oils,including base oils comprising one or more estolides.

In certain embodiments, the compositions comprising one or moreestolides are partially or fully biodegradable and thereby posediminished risk to the environment. In certain embodiments, thecompositions meet guidelines set for by the Organization for EconomicCooperation and Development (OECD) for degradation and accumulationtesting. The OECD has indicated that several tests may be used todetermine the “ready biodegradability” of organic chemicals. Aerobicready biodegradability by OECD 301D measures the mineralization of thetest sample to CO₂ in closed aerobic microcosms that simulate an aerobicaquatic environment, with microorganisms seeded from a waste-watertreatment plant. OECD 301D is considered representative of most aerobicenvironments that are likely to receive waste materials. Aerobic“ultimate biodegradability” can be determined by OECD 302D. Under OECD302D, microorganisms are pre-acclimated to biodegradation of the testmaterial during a pre-incubation period, then incubated in sealedvessels with relatively high concentrations of microorganisms andenriched mineral salts medium. OECD 302D ultimately determines whetherthe test materials are completely biodegradable, albeit under lessstringent conditions than “ready biodegradability” assays.

As used in the present specification, the following words, phrases andsymbols are generally intended to have the meanings as set forth below,except to the extent that the context in which they are used indicatesotherwise. The following abbreviations and terms have the indicatedmeanings throughout:

A dash (“-”) that is not between two letters or symbols is used toindicate a point of attachment for a substituent. For example, —C(O)NH₂is attached through the carbon atom.

“Alkoxy” by itself or as part of another substituent refers to a radical—OR³¹ where R³¹ is alkyl, cycloalkyl, cycloalkylalkyl, aryl, orarylalkyl, which can be substituted, as defined herein. In someembodiments, alkoxy groups have from 1 to 8 carbon atoms. In someembodiments, alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.Examples of alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.

“Alkyl” by itself or as part of another substituent refers to asaturated or unsaturated, branched, or straight-chain monovalenthydrocarbon radical derived by the removal of one hydrogen atom from asingle carbon atom of a parent alkane, alkene, or alkyne. Examples ofalkyl groups include, but are not limited to, methyl; ethyls such asethanyl, ethenyl, and ethynyl; propyls such as propan-1-yl, propan-2-yl,prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-1-yn-1-yl,prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl,2-methyl-propan-1-yl, 2-methyl-propan-2-yl, but-1-en-1-yl,but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl,buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, but-1-yn-1-yl, but-1-yn-3-yl,but-3-yn-1-yl, etc.; and the like.

Unless otherwise indicated, the term “alkyl” is specifically intended toinclude groups having any degree or level of saturation, i.e., groupshaving exclusively single carbon-carbon bonds, groups having one or moredouble carbon-carbon bonds, groups having one or more triplecarbon-carbon bonds, and groups having mixtures of single, double, andtriple carbon-carbon bonds. Where a specific level of saturation isintended, the terms “alkanyl,” “alkenyl,” and “alkynyl” are used. Incertain embodiments, an alkyl group comprises from 1 to 40 carbon atoms,in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certainembodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certainembodiments from 1 to 6 or 1 to 3 carbon atoms. In certain embodiments,an alkyl group comprises from 8 to 22 carbon atoms, in certainembodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkylgroup comprises from 3 to 20 or 7 to 17 carbons. In some embodiments,the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon radical derived by the removal of onehydrogen atom from a single carbon atom of a parent aromatic ringsystem. Aryl encompasses 5- and 6-membered carbocyclic aromatic rings,for example, benzene; bicyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, naphthalene, indane, andtetralin; and tricyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, fluorene. Aryl encompassesmultiple ring systems having at least one carbocyclic aromatic ringfused to at least one carbocyclic aromatic ring, cycloalkyl ring, orheterocycloalkyl ring. For example, aryl includes 5- and 6-memberedcarbocyclic aromatic rings fused to a 5- to 7-membered non-aromaticheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexalene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, an aryl group cancomprise from 5 to 20 carbon atoms, and in certain embodiments, from 5to 12 carbon atoms. In certain embodiments, an aryl group can comprise5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbonatoms. Aryl, however, does not encompass or overlap in any way withheteroaryl, separately defined herein. Hence, a multiple ring system inwhich one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Examples of arylalkyl groups include, but are not limitedto, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl, and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl, or arylalkynylis used. In certain embodiments, an arylalkyl group is C₇₋₃₀ arylalkyl,e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group isC₁₋₁₀ and the aryl moiety is C₆₋₂₀, and in certain embodiments, anarylalkyl group is C₇₋₂₀ arylalkyl, e.g., the alkanyl, alkenyl, oralkynyl moiety of the arylalkyl group is C₁₋₈ and the aryl moiety isC₆₋₁₂.

Estolide “base oil” and “base stock”, unless otherwise indicated, referto any composition comprising one or more estolide compounds. It shouldbe understood that an estolide “base oil” or “base stock” is not limitedto compositions for a particular use, and may generally refer tocompositions comprising one or more estolides, including mixtures ofestolides. Estolide base oils and base stocks can also include compoundsother than estolides.

“Compounds” refers to compounds encompassed by structural Formula I, II,and III herein and includes any specific compounds within the formulawhose structure is disclosed herein. Compounds may be identified eitherby their chemical structure and/or chemical name. When the chemicalstructure and chemical name conflict, the chemical structure isdeterminative of the identity of the compound. The compounds describedherein may contain one or more chiral centers and/or double bonds andtherefore may exist as stereoisomers such as double-bond isomers (i.e.,geometric isomers), enantiomers, or diastereomers. Accordingly, anychemical structures within the scope of the specification depicted, inwhole or in part, with a relative configuration encompass all possibleenantiomers and stereoisomers of the illustrated compounds including thestereoisomerically pure form (e.g., geometrically pure, enantiomericallypure, or diastereomerically pure) and enantiomeric and stereoisomericmixtures. Enantiomeric and stereoisomeric mixtures may be resolved intotheir component enantiomers or stereoisomers using separation techniquesor chiral synthesis techniques well known to the skilled artisan.

For the purposes of the present disclosure, “chiral compounds” arecompounds having at least one center of chirality (i.e. at least oneasymmetric atom, in particular at least one asymmetric C atom), havingan axis of chirality, a plane of chirality or a screw structure.“Achiral compounds” are compounds which are not chiral.

Compounds of Formula I, II, and III include, but are not limited to,optical isomers of compounds of Formula I, II, and III, racematesthereof, and other mixtures thereof. In such embodiments, the singleenantiomers or diastereomers, i.e., optically active forms, can beobtained by asymmetric synthesis or by resolution of the racemates.Resolution of the racemates may be accomplished by, for example,chromatography, using, for example a chiral high-pressure liquidchromatography (HPLC) column. However, unless otherwise stated, itshould be assumed that Formula I, II, and III cover all asymmetricvariants of the compounds described herein, including isomers,racemates, enantiomers, diastereomers, and other mixtures thereof. Inaddition, compounds of Formula I, II and III include Z- and E-forms(e.g., cis- and trans-forms) of compounds with double bonds. Thecompounds of Formula I, II, and III may also exist in several tautomericforms including the enol form, the keto form, and mixtures thereof.Accordingly, the chemical structures depicted herein encompass allpossible tautomeric forms of the illustrated compounds.

“Cycloalkyl” by itself or as part of another substituent refers to asaturated or unsaturated cyclic alkyl radical. Where a specific level ofsaturation is intended, the nomenclature “cycloalkanyl” or“cycloalkenyl” is used. Examples of cycloalkyl groups include, but arenot limited to, groups derived from cyclopropane, cyclobutane,cyclopentane, cyclohexane, and the like. In certain embodiments, acycloalkyl group is C₃₋₁₅ cycloalkyl, and in certain embodiments, C₃₋₁₂cycloalkyl or C₅₋₁₂ cycloalkyl. In certain embodiments, a cycloalkylgroup is a C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, or C₁₅cycloalkyl.

“Cycloalkylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with acycloalkyl group. Where specific alkyl moieties are intended, thenomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynylis used. In certain embodiments, a cycloalkylalkyl group is C₇₋₃₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₁₀ and the cycloalkyl moiety is C₆₋₂₀, andin certain embodiments, a cycloalkylalkyl group is C₇₋₂₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₈ and the cycloalkyl moiety is C₄₋₂₀ orC₆₋₁₂.

“Halogen” refers to a fluoro, chloro, bromo, or iodo group.

“Heteroaryl” by itself or as part of another substituent refers to amonovalent heteroaromatic radical derived by the removal of one hydrogenatom from a single atom of a parent heteroaromatic ring system.Heteroaryl encompasses multiple ring systems having at least onearomatic ring fused to at least one other ring, which can be aromatic ornon-aromatic in which at least one ring atom is a heteroatom. Heteroarylencompasses 5- to 12-membered aromatic, such as 5- to 7-membered,monocyclic rings containing one or more, for example, from 1 to 4, or incertain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S,with the remaining ring atoms being carbon; and bicyclicheterocycloalkyl rings containing one or more, for example, from 1 to 4,or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O,and S, with the remaining ring atoms being carbon and wherein at leastone heteroatom is present in an aromatic ring. For example, heteroarylincludes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a5- to 7-membered cycloalkyl ring. For such fused, bicyclic heteroarylring systems wherein only one of the rings contains one or moreheteroatoms, the point of attachment may be at the heteroaromatic ringor the cycloalkyl ring. In certain embodiments, when the total number ofN, S, and O atoms in the heteroaryl group exceeds one, the heteroatomsare not adjacent to one another. In certain embodiments, the totalnumber of N, S, and O atoms in the heteroaryl group is not more thantwo. In certain embodiments, the total number of N, S, and O atoms inthe aromatic heterocycle is not more than one. Heteroaryl does notencompass or overlap with aryl as defined herein.

Examples of heteroaryl groups include, but are not limited to, groupsderived from acridine, arsindole, carbazole, β-carboline, chromane,chromene, cinnoline, furan, imidazole, indazole, indole, indoline,indolizine, isobenzofuran, isochromene, isoindole, isoindoline,isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole,oxazole, perimidine, phenanthridine, phenanthroline, phenazine,phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine,pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline,quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene,triazole, xanthene, and the like. In certain embodiments, a heteroarylgroup is from 5- to 20-membered heteroaryl, and in certain embodimentsfrom 5- to 12-membered heteroaryl or from 5- to 10-membered heteroaryl.In certain embodiments, a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.In certain embodiments heteroaryl groups are those derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, and pyrazine.

“Heteroarylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynylis used. In certain embodiments, a heteroarylalkyl group is a 6- to30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 10-membered and the heteroarylmoiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6-to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 8-membered and the heteroarylmoiety is a 5- to 12-membered heteroaryl.

“Heterocycloalkyl” by itself or as part of another substituent refers toa partially saturated or unsaturated cyclic alkyl radical in which oneor more carbon atoms (and any associated hydrogen atoms) areindependently replaced with the same or different heteroatom. Examplesof heteroatoms to replace the carbon atom(s) include, but are notlimited to, N, P, O, S, Si, etc. Where a specific level of saturation isintended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl”is used. Examples of heterocycloalkyl groups include, but are notlimited to, groups derived from epoxides, azirines, thiiranes,imidazolidine, morpholine, piperazine, piperidine, pyrazolidine,pyrrolidine, quinuclidine, and the like.

“Heterocycloalkylalkyl” by itself or as part of another substituentrefers to an acyclic alkyl radical in which one of the hydrogen atomsbonded to a carbon atom, typically a terminal or sp³ carbon atom, isreplaced with a heterocycloalkyl group. Where specific alkyl moietiesare intended, the nomenclature heterocycloalkylalkanyl,heterocycloalkylalkenyl, or heterocycloalkylalkynyl is used. In certainembodiments, a heterocycloalkylalkyl group is a 6- to 30-memberedheterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety ofthe heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkylmoiety is a 5- to 20-membered heterocycloalkyl, and in certainembodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl,alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to8-membered and the heterocycloalkyl moiety is a 5- to 12-memberedheterocycloalkyl.

“Mixture” refers to a collection of molecules or chemical substances.Each component in a mixture can be independently varied. A mixture maycontain, or consist essentially of, two or more substances intermingledwith or without a constant percentage composition, wherein eachcomponent may or may not retain its essential original properties, andwhere molecular phase mixing may or may not occur. In mixtures, thecomponents making up the mixture may or may not remain distinguishablefrom each other by virtue of their chemical structure.

“Parent aromatic ring system” refers to an unsaturated cyclic orpolycyclic ring system having a conjugated π (pi) electron system.Included within the definition of “parent aromatic ring system” arefused ring systems in which one or more of the rings are aromatic andone or more of the rings are saturated or unsaturated, such as, forexample, fluorene, indane, indene, phenalene, etc. Examples of parentaromatic ring systems include, but are not limited to, aceanthrylene,acenaphthylene, acephenanthrylene, anthracene, azulene, benzene,chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene,hexalene, as-indacene, s-indacene, indane, indene, naphthalene,octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene,pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene,and the like.

“Parent heteroaromatic ring system” refers to a parent aromatic ringsystem in which one or more carbon atoms (and any associated hydrogenatoms) are independently replaced with the same or different heteroatom.Examples of heteroatoms to replace the carbon atoms include, but are notlimited to, N, P, O, S, Si, etc. Specifically included within thedefinition of “parent heteroaromatic ring systems” are fused ringsystems in which one or more of the rings are aromatic and one or moreof the rings are saturated or unsaturated, such as, for example,arsindole, benzodioxan, benzofuran, chromane, chromene, indole,indoline, xanthene, etc. Examples of parent heteroaromatic ring systemsinclude, but are not limited to, arsindole, carbazole, β-carboline,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like.

“Substituted” refers to a group in which one or more hydrogen atoms areindependently replaced with the same or different substituent(s).Examples of substituents include, but are not limited to, —R⁶⁴, —R⁶⁰,—O⁻, —OH, ═O, —OR⁶⁰, —SR⁶⁰, —S—, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CN, —CF₃, —OCN,—SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂OH, —S(O)₂R⁶⁰, —OS(O₂)O⁻,—OS(O)₂R⁶⁰, —P(O)(O⁻)₂, —P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰,—C(S)R⁶⁰, —C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻, —C(S)OR⁶⁰, —NR⁶²C(O)NR⁶⁰R⁶¹,—NR⁶²C(S)NR⁶⁰R⁶¹, —NR⁶²C(NR⁶³)NR⁶⁰R⁶¹, —C(NR⁶²)NR⁶⁰R⁶¹, —S(O)₂, NR⁶⁰R⁶¹,—NR⁶³S(O)₂R⁶⁰, —NR⁶³C(O)R⁶⁰, and —S(O)R⁶⁰;

wherein each —R⁶⁴ is independently a halogen; each R⁶⁰ and R⁶¹ areindependently alkyl, substituted alkyl, alkoxy, substituted alkoxy,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, orsubstituted heteroarylalkyl, or R⁶⁰ and R⁶¹ together with the nitrogenatom to which they are bonded form a heterocycloalkyl, substitutedheterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R⁶²and R⁶³ are independently alkyl, substituted alkyl, aryl, substitutedaryl, arylalkyl, substituted arylalkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl,or R⁶² and R⁶³ together with the atom to which they are bonded form oneor more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, orsubstituted heteroaryl rings;

wherein the “substituted” substituents, as defined above for R⁶⁰, R⁶¹,R⁶², and R⁶³, are substituted with one or more, such as one, two, orthree, groups independently selected from alkyl, -alkyl-OH,—O-haloalkyl, -alkyl-NH₂, alkoxy, cycloalkyl, cycloalkylalkyl,heterocycloalkyl, heterocycloalkylalkyl, aryl, heteroaryl, arylalkyl,heteroarylalkyl, —O⁻, —OH, ═O, —O-alkyl, —O-aryl, —O-heteroarylalkyl,—O-cycloalkyl, —O-heterocycloalkyl, —SH, —S—, ═S, —S— alkyl, —S-aryl,—S-heteroarylalkyl, —S-cycloalkyl, —S-heterocycloalkyl, —NH₂, ═NH, —CN,—CF₃, —OCN, —SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂, —S(O)₂OH,—OS(O₂)O⁻, —SO₂(alkyl), —SO₂(phenyl), —SO₂(haloalkyl), —SO₂NH₂,—SO₂NH(alkyl), —SO₂NH(phenyl), —P(O)(O⁻)₂, —P(O)(O-alkyl)(O⁻),—OP(O)(O-alkyl)(O-alkyl), —CO₂H, —C(O)O(alkyl), —CON(alkyl)(alkyl),—CONH(alkyl), —CONH₂, —C(O)(alkyl), —C(O)(phenyl), —C(O)(haloalkyl),—OC(O)(alkyl), —N(alkyl)(alkyl), —NH(alkyl), —N(alkyl)(alkylphenyl),—NH(alkylphenyl), —NHC(O)(alkyl), —NHC(O)(phenyl), —N(alkyl)C(O)(alkyl),and —N(alkyl)C(O)(phenyl).

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

All numerical ranges herein include all numerical values and ranges ofall numerical values within the recited range of numerical values.

The present disclosure relates to estolide compounds, compositions andmethods of making the same. In certain embodiments, the presentdisclosure also relates to estolide compounds, compositions comprisingestolide compounds, the synthesis of such compounds, and the formulationof such compositions. In certain embodiments, the present disclosurerelates to biosynthetic estolides having desired viscometric properties,while retaining or even improving other properties such as oxidativestability and pour point. In certain embodiments, new methods ofpreparing estolide compounds exhibiting such properties are provided.The present disclosure also relates to lubricant andlubricant-containing compositions.

In certain embodiments the composition comprises at least one estolidecompound of Formula I:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, and 12;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted.

In certain embodiments the composition comprises at least one estolidecompound of Formula II:

-   -   m is an integer greater than or equal to 1;    -   n is an integer greater than or equal to 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched.

In certain embodiments the composition comprises at least one estolidecompound of Formula III:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0 to 20;    -   y is, independently for each occurrence, an integer selected        from 0 to 20;    -   n is an integer greater than or equal to 0;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched;    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted.

In certain embodiments, the composition comprises at least one estolidecompound of Formula I, II, or III where R₁ is hydrogen.

The terms “chain” or “fatty acid chain” or “fatty acid chain residue,”as used with respect to the estolide compounds of Formula I, II, andIII, refer to one or more of the fatty acid residues incorporated inestolide compounds, e.g., R₃ or R₄ of Formula II, or the structuresrepresented by CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— in Formula I and III.

The R₁ in Formula I, II, and III at the top of each Formula shown is anexample of what may be referred to as a “cap” or “capping material,” asit “caps” the top of the estolide. Similarly, the capping group may bean organic acid residue of general formula —OC(O)-alkyl, i.e., acarboxylic acid with a substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched alkyl as defined herein, or aformic acid residue. In certain embodiments, the “cap” or “cappinggroup” is a fatty acid. In certain embodiments, the capping group,regardless of size, is substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched. The cap or capping materialmay also be referred to as the primary or alpha (a) chain.

Depending on the manner in which the estolide is synthesized, the cap orcapping group alkyl may be the only alkyl from an organic acid residuein the resulting estolide that is unsaturated. In certain embodiments,it may be desirable to use a saturated organic or fatty-acid cap toincrease the overall saturation of the estolide and/or to increase theresulting estolide's stability. For example, in certain embodiments, itmay be desirable to provide a method of providing a saturated cappedestolide by hydrogenating an unsaturated cap using any suitable methodsavailable to those of ordinary skill in the art. Hydrogenation may beused with various sources of the fatty-acid feedstock, which may includemono- and/or polyunsaturated fatty acids. Without being bound to anyparticular theory, in certain embodiments, hydrogenating the estolidemay help to improve the overall stability of the molecule. However, afully-hydrogenated estolide, such as an estolide with a larger fattyacid cap, may exhibit increased pour point temperatures. In certainembodiments, it may be desirable to offset any loss in desirablepour-point characteristics by using shorter, saturated cappingmaterials.

The R₄C(O)O— of Formula II or structure CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— ofFormula I and III serve as the “base” or “base chain residue” of theestolide. Depending on the manner in which the estolide is synthesized,the base organic acid or fatty acid residue may be the only residue thatremains in its free-acid form after the initial synthesis of theestolide. However, in certain embodiments, in an effort to alter orimprove the properties of the estolide, the free acid may be reactedwith any number of substituents. For example, it may be desirable toreact the free acid estolide with alcohols, glycols, amines, or othersuitable reactants to provide the corresponding ester, amide, or otherreaction products. The base or base chain residue may also be referredto as tertiary or gamma (γ) chains.

The R₃C(O)O— of Formula II or structure CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— ofFormula I and III are linking residues that link the capping materialand the base fatty-acid residue together. There may be any number oflinking residues in the estolide, including when n=0 and the estolide isin its dimer form. Depending on the manner in which the estolide isprepared, a linking residue may be a fatty acid and may initially be inan unsaturated form during synthesis. In some embodiments, the estolidewill be formed when a catalyst is used to produce a carbocation at thefatty acid's site of unsaturation, which is followed by nucleophilicattack on the carbocation by the carboxylic group of another fatty acid.In some embodiments, it may be desirable to have a linking fatty acidthat is monounsaturated so that when the fatty acids link together, allof the sites of unsaturation are eliminated. The linking residue(s) mayalso be referred to as secondary or beta (β) chains.

In certain embodiments, the cap is an acetyl group, the linkingresidue(s) is one or more fatty acid residues, and the base chainresidue is a fatty acid residue. In certain embodiments, the linkingresidues present in an estolide differ from one another. In certainembodiments, one or more of the linking residues differs from the basechain residue.

As noted above, in certain embodiments, suitable unsaturated fatty acidsfor preparing the estolides may include any mono- or polyunsaturatedfatty acid. For example, monounsaturated fatty acids, along with asuitable catalyst, will form a single carbocation that allows for theaddition of a second fatty acid, whereby a single link between two fattyacids is formed. Suitable monounsaturated fatty acids may include, butare not limited to, palmitoleic acid (16:1), vaccenic acid (18:1), oleicacid (18:1), eicosenoic acid (20:1), erucic acid (22:1), and nervonicacid (24:1). In addition, in certain embodiments, polyunsaturated fattyacids may be used to create estolides. Suitable polyunsaturated fattyacids may include, but are not limited to, hexadecatrienoic acid (16:3),alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoicacid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),heneicosapentaenoic acid (21:5), docosapentaenoic acid (22:5),docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5),tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleicacid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid(20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid(22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4),tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid(20:3), rumenic acid (18:2), alpha-calendic acid (18:3), beta-calendicacid (18:3), jacaric acid (18:3), alpha-eleostearic acid (18:3),beta-eleostearic (18:3), catalpic acid (18:3), punicic acid (18:3),rumelenic acid (18:3), alpha-parinaric acid (18:4), beta-parinaric acid(18:4), and bosseopentaenoic acid (20:5). In certain embodiments,hydroxy fatty acids may be polymerized or homopolymerized by reactingthe carboxylic acid functionality of one fatty acid with the hydroxyfunctionality of a second fatty acid. Exemplary hydroxyl fatty acidsinclude, but are not limited to, ricinoleic acid, 6-hydroxystearic acid,9,10-dihydroxystearic acid, 12-hydroxystearic acid, and14-hydroxystearic acid.

The process for preparing the estolide compounds described herein mayinclude the use of any natural or synthetic fatty acid source. However,it may be desirable to source the fatty acids from a renewablebiological feedstock. For example, suitable starting materials ofbiological origin include, but are not limited to, plant fats, plantoils, plant waxes, animal fats, animal oils, animal waxes, fish fats,fish oils, fish waxes, algal oils and mixtures of two or more thereof.Other potential fatty acid sources include, but are not limited to,waste and recycled food-grade fats and oils, fats, oils, and waxesobtained by genetic engineering, fossil fuel-based materials and othersources of the materials desired.

In some embodiments, the estolide comprises fatty-acid chains of varyinglengths. In some embodiments, x is, independently for each occurrence,an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1to 10, 2 to 8, 6 to 8, or 4 to 6. In some embodiments, x is,independently for each occurrence, an integer selected from 7 and 8. Insome embodiments, x is, independently for each occurrence, an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20.

In some embodiments, y is, independently for each occurrence, an integerselected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to8, 6 to 8, or 4 to 6. In some embodiments, y is, independently for eachoccurrence, an integer selected from 7 and 8. In some embodiments, y is,independently for each occurrence, an integer selected from 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

In some embodiments, x+y is, independently for each chain, an integerselected from 0 to 40, 0 to 20, 10 to 20, or 12 to 18. In someembodiments, x+y is, independently for each chain, an integer selectedfrom 13 to 15. In some embodiments, x+y is 15. In some embodiments, x+yis, independently for each chain, an integer selected from 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24.

In some embodiments, the estolide compound of Formula I, II, or III maycomprise any number of fatty acid residues to form an “n-mer” estolide.For example, the estolide may be in its dimer (n=0), trimer (n=1),tetramer (n=2), pentamer (n=3), hexamer (n=4), heptamer (n=5), octamer(n=6), nonamer (n=7), or decamer (n=8) form. In some embodiments, n isan integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 0 to 12, 0to 10, 0 to 8, or 0 to 6. In some embodiments, n is an integer selectedfrom 0 to 4. In some embodiments, n is 1, wherein said at least onecompound of Formula I, II, or III comprises the trimer. In someembodiments, n is greater than 1. In some embodiments, n is an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20.

In some embodiments, R₁ of Formula I, II, or III is an optionallysubstituted alkyl that is saturated or unsaturated, and branched orunbranched. In some embodiments, the alkyl group is a C₁ to C₄₀ alkyl,C₁ to C₂₂ alkyl or C₁ to C₁₈ alkyl. In some embodiments, the alkyl groupis selected from C₇ to C₁₇ alkyl. In some embodiments, R₁ is selectedfrom C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl.In some embodiments, R₁ is selected from C₁₃ to C₁₇ alkyl, such as fromC₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₁ is a C₁,C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇,C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₂ of Formula I, II, or III is an optionallysubstituted alkyl that is saturated or unsaturated, and branched orunbranched. In some embodiments, the alkyl group is a C₁ to C₄₀ alkyl,C₁ to C₂₂ alkyl or C₁ to C₁₈ alkyl. In some embodiments, the alkyl groupis selected from C₇ to C₁₇ alkyl. In some embodiments, R₂ is selectedfrom C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl.In some embodiments, R₂ is selected from C₁₃ to C₁₇ alkyl, such as fromC₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₂ is a C₁,C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇,C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₃ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₃ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₃ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₃ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₄ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₄ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₄ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₄ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

As noted above, in certain embodiments, it may be possible to manipulateone or more of the estolides' properties by altering the length of R₁and/or its degree of saturation. However, in certain embodiments, thelevel of substitution on R₁ may also be altered to change or evenimprove the estolides' properties. Without being bound to any particulartheory, in certain embodiments, it is believed that the presence ofpolar substituents on R₁, such as one or more hydroxy groups, mayincrease the viscosity of the estolide, while increasing pour point.Accordingly, in some embodiments, R₁ will be unsubstituted or optionallysubstituted with a group that is not hydroxyl.

In some embodiments, the estolide is in its free-acid form, wherein R₂of Formula I, II, or III is hydrogen. In some embodiments, R₂ isselected from optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched. In certain embodiments, the R₂residue may comprise any desired alkyl group, such as those derived fromesterification of the estolide with the alcohols identified in theexamples herein. In some embodiments, the alkyl group is selected fromC₁ to C₄₀, C₁ to C₂₂, C₃ to C₂₀, C₁ to C₁₈, or C₆ to C₁₂ alkyl. In someembodiments, R₂ may be selected from C₃ alkyl, C₄ alkyl, C₈ alkyl, C₁₂alkyl, C₁₆ alkyl, C₁₈ alkyl, and C₂₀ alkyl. For example, in certainembodiments, R₂ may be branched, such as isopropyl, isobutyl, or2-ethylhexyl. In some embodiments, R₂ may be a larger alkyl group,branched or unbranched, comprising C₁₂ alkyl, C₁₆ alkyl, C₁₈ alkyl, orC₂₀ alkyl. Such groups at the R₂ position may be derived fromesterification of the free-acid estolide using the Jarcol™ line ofalcohols marketed by Jarchem Industries, Inc. of Newark, N.J., includingJarcol™ I-18CG, I-20, I-12, I-16, I-18T, and 85BJ. In some cases, R₂ maybe sourced from certain alcohols to provide branched alkyls such asisostearyl and isopalmityl. It should be understood that suchisopalmityl and isostearyl akyl groups may cover any branched variationof C₁₆ and C₁₈, respectively. For example, the estolides describedherein may comprise highly-branched isopalmityl or isostearyl groups atthe R₂ position, derived from the Fineoxocol® line of isopalmityl andisostearyl alcohols marketed by Nissan Chemical America Corporation ofHouston, Tex., including Fineoxocol® 180, 180N, and 1600. Without beingbound to any particular theory, in certain embodiments, large,highly-branched alkyl groups (e.g., isopalmityl and isostearyl) at theR₂ position of the estolides can provide at least one way to increase anestolide-containing composition's viscosity, while substantiallyretaining or even reducing its pour point.

In some embodiments, the compounds described herein may comprise amixture of two or more estolide compounds of Formula I, II, and III. Itis possible to characterize the chemical makeup of an estolide, amixture of estolides, or a composition comprising estolides, by usingthe compound's, mixture's, or composition's measured estolide number(EN) of compound or composition. The EN represents the average number offatty acids added to the base fatty acid. The EN also represents theaverage number of estolide linkages per molecule:EN=n+1wherein n is the number of secondary (β) fatty acids. Accordingly, asingle estolide compound will have an EN that is a whole number, forexample for dimers, trimers, and tetramers:

-   -   dimer EN=1    -   trimer EN=2    -   tetramer EN=3

However, a composition comprising two or more estolide compounds mayhave an EN that is a whole number or a fraction of a whole number. Forexample, a composition having a 1:1 molar ratio of dimer and trimerwould have an EN of 1.5, while a composition having a 1:1 molar ratio oftetramer and trimer would have an EN of 2.5.

In some embodiments, the compositions may comprise a mixture of two ormore estolides having an EN that is an integer or fraction of an integerthat is greater than 4.5, or even 5.0. In some embodiments, the EN maybe an integer or fraction of an integer selected from about 1.0 to about5.0. In some embodiments, the EN is an integer or fraction of an integerselected from 1.2 to about 4.5. In some embodiments, the EN is selectedfrom a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4,5.6 and 5.8. In some embodiments, the EN is selected from a value lessthan 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6,3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0. Insome embodiments, the EN is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.0,2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8,5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.

As noted above, it should be understood that the chains of the estolidecompounds may be independently optionally substituted, wherein one ormore hydrogens are removed and replaced with one or more of thesubstituents identified herein. Similarly, two or more of the hydrogenresidues may be removed to provide one or more sites of unsaturation,such as a cis or trans double bond. Further, the chains may optionallycomprise branched hydrocarbon residues. For example, in some embodimentsthe estolides described herein may comprise at least one compound ofFormula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched.

In certain embodiments, m is 1. In some embodiments, m is an integerselected from 2, 3, 4, and 5. In some embodiments, n is an integerselected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. In someembodiments, one or more R₃ differs from one or more other R₃ in acompound of Formula II. In some embodiments, one or more R₃ differs fromR₄ in a compound of Formula II. In some embodiments, if the compounds ofFormula II are prepared from one or more polyunsaturated fatty acids, itis possible that one or more of R₃ and R₄ will have one or more sites ofunsaturation. In some embodiments, if the compounds of Formula II areprepared from one or more branched fatty acids, it is possible that oneor more of R₃ and R₄ will be branched.

In some embodiments, R₃ and R₄ can be CH₃(CH₂)_(y)CH(CH₂)_(x)—, where xis, independently for each occurrence, an integer selected from 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, andy is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.Where both R₃ and R₄ are CH₃(CH₂)_(y)CH(CH₂)_(x)—, the compounds may becompounds according to Formula I and III.

Without being bound to any particular theory, in certain embodiments,altering the EN produces estolide-containing compositions having desiredviscometric properties while substantially retaining or even reducingpour point. For example, in some embodiments the estolides exhibit adecreased pour point upon increasing the EN value. Accordingly, incertain embodiments, a method is provided for retaining or decreasingthe pour point of an estolide base oil by increasing the EN of the baseoil, or a method is provided for retaining or decreasing the pour pointof a composition comprising an estolide base oil by increasing the EN ofthe base oil. In some embodiments, the method comprises: selecting anestolide base oil having an initial EN and an initial pour point; andremoving at least a portion of the base oil, said portion exhibiting anEN that is less than the initial EN of the base oil, wherein theresulting estolide base oil exhibits an EN that is greater than theinitial EN of the base oil, and a pour point that is equal to or lowerthan the initial pour point of the base oil. In some embodiments, theselected estolide base oil is prepared by oligomerizing at least onefirst unsaturated fatty acid with at least one second unsaturated fattyacid and/or saturated fatty acid. In some embodiments, the removing atleast a portion of the base oil or a composition comprising two or moreestolide compounds is accomplished by use of at least one ofdistillation, chromatography, membrane separation, phase separation,affinity separation, and solvent extraction. In some embodiments, thedistillation takes place at a temperature and/or pressure that issuitable to separate the estolide base oil or a composition comprisingtwo or more estolide compounds into different “cuts” that individuallyexhibit different EN values. In some embodiments, this may beaccomplished by subjecting the base oil or a composition comprising twoor more estolide compounds to a temperature of at least about 250° C.and an absolute pressure of no greater than about 25 microns. In someembodiments, the distillation takes place at a temperature range ofabout 250° C. to about 310° C. and an absolute pressure range of about10 microns to about 25 microns.

In some embodiments, estolide compounds and compositions exhibit an ENthat is greater than or equal to 1, such as an integer or fraction of aninteger selected from about 1.0 to about 2.0. In some embodiments, theEN is an integer or fraction of an integer selected from about 1.0 toabout 1.6. In some embodiments, the EN is a fraction of an integerselected from about 1.1 to about 1.5. In some embodiments, the EN isselected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, and 1.9. In some embodiments, the EN is selected from a valueless than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

In some embodiments, the EN is greater than or equal to 1.5, such as aninteger or fraction of an integer selected from about 1.8 to about 2.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.0 to about 2.6. In some embodiments, the EN is afraction of an integer selected from about 2.1 to about 2.5. In someembodiments, the EN is selected from a value greater than 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, and 2.7. In some embodiments, the EN isselected from a value less than 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, and 2.8. In some embodiments, the EN is about 1.8, 2.0, 2.2, 2.4,2.6, or 2.8.

In some embodiments, the EN is greater than or equal to about 4, such asan integer or fraction of an integer selected from about 4.0 to about5.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 4.2 to about 4.8. In some embodiments, the EN is a fractionof an integer selected from about 4.3 to about 4.7. In some embodiments,the EN is selected from a value greater than 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, and 4.9. In some embodiments, the EN is selectedfrom a value less than 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and5.0. In some embodiments, the EN is about 4.0, 4.2, 4.4, 4.6, 4.8, or5.0.

In some embodiments, the EN is greater than or equal to about 5, such asan integer or fraction of an integer selected from about 5.0 to about6.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 5.2 to about 5.8. In some embodiments, the EN is a fractionof an integer selected from about 5.3 to about 5.7. In some embodiments,the EN is selected from a value greater than 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, and 5.9. In some embodiments, the EN is selectedfrom a value less than 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and6.0. In some embodiments, the EN is about 5.0, 5.2, 5.4, 5.4, 5.6, 5.8,or 6.0.

In some embodiments, the EN is greater than or equal to 1, such as aninteger or fraction of an integer selected from about 1.0 to about 2.0.In some embodiments, the EN is a fraction of an integer selected fromabout 1.1 to about 1.7. In some embodiments, the EN is a fraction of aninteger selected from about 1.1 to about 1.5. In some embodiments, theEN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5,1.6, 1.7, 1.8, or 1.9. In some embodiments, the EN is selected from avalue less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In someembodiments, the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. In someembodiments, the EN is greater than or equal to 1, such as an integer orfraction of an integer selected from about 1.2 to about 2.2. In someembodiments, the EN is an integer or fraction of an integer selectedfrom about 1.4 to about 2.0. In some embodiments, the EN is a fractionof an integer selected from about 1.5 to about 1.9. In some embodiments,the EN is selected from a value greater than 1.0, 1.1. 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.1. In some embodiments, the EN isselected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, and 2.2. In some embodiments, the EN is about 1.0, 1.2, 1.4,1.6, 1.8, 2.0, or 2.2.

In some embodiments, the EN is greater than or equal to 2, such as aninteger or fraction of an integer selected from about 2.8 to about 3.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.9 to about 3.5. In some embodiments, the EN is aninteger or fraction of an integer selected from about 3.0 to about 3.4.In some embodiments, the EN is selected from a value greater than 2.0,2.1, 2.2., 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4, 3.5, 3.6, and3.7. In some embodiments, the EN is selected from a value less than 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, and 3.8. In some embodiments, the EN is about 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, or 3.8. Typically, base stocks andestolide-containing compositions exhibit certain lubricity, viscosity,and/or pour point characteristics. For example, in certain embodiments,the base oils, compounds, and compositions may exhibit viscosities thatrange from about 10 cSt to about 250 cSt at 40° C., and/or about 3 cStto about 30 cSt at 100° C. In some embodiments, the base oils,compounds, and compositions may exhibit viscosities within a range fromabout 50 cSt to about 150 cSt at 40° C., and/or about 10 cSt to about 20cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 55 cSt at 40° C. or less than about 45 cStat 40° C., and/or less than about 12 cSt at 100° C. or less than about10 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 25 cSt toabout 55 cSt at 40° C., and/or about 5 cSt to about 11 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 35 cSt to about 45 cSt at 40° C.,and/or about 6 cSt to about 10 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 38 cSt to about 43 cSt at 40° C., and/or about 7 cSt toabout 9 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 120 cSt at 40° C. or less than about 100 cStat 40° C., and/or less than about 18 cSt at 100° C. or less than about17 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 70 cSt toabout 120 cSt at 40° C., and/or about 12 cSt to about 18 cSt at 100° C.In some embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 80 cSt to about 100 cSt at 40° C.,and/or about 13 cSt to about 17 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 85 cSt to about 95 cSt at 40° C., and/or about 14 cStto about 16 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 180 cSt at 40° C. or greater than about200 cSt at 40° C., and/or greater than about 20 cSt at 100° C. orgreater than about 25 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 180 cSt to about 230 cSt at 40° C., and/or about 25 cSt to about31 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 200 cStto about 250 cSt at 40° C., and/or about 25 cSt to about 35 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 210 cSt to about 230 cStat 40° C., and/or about 28 cSt to about 33 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 200 cSt to about 220 cSt at 40°C., and/or about 26 cSt to about 30 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities within arange from about 205 cSt to about 215 cSt at 40° C., and/or about 27 cStto about 29 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 45 cSt at 40° C. or less than about 38 cStat 40° C., and/or less than about 10 cSt at 100° C. or less than about 9cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 20 cSt toabout 45 cSt at 40° C., and/or about 4 cSt to about 10 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 28 cSt to about 38 cSt at 40° C.,and/or about 5 cSt to about 9 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 30 cSt to about 35 cSt at 40° C., and/or about 6 cSt toabout 8 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 80 cSt at 40° C. or less than about 70 cStat 40° C., and/or less than about 14 cSt at 100° C. or less than about13 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 50 cSt toabout 80 cSt at 40° C., and/or about 8 cSt to about 14 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 60 cSt to about 70 cSt at 40° C.,and/or about 9 cSt to about 13 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 63 cSt to about 68 cSt at 40° C., and/or about 10 cStto about 12 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 120 cSt at 40° C. or greater than about130 cSt at 40° C., and/or greater than about 15 cSt at 100° C. orgreater than about 18 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 120 cSt to about 150 cSt at 40° C., and/or about 16 cSt to about24 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 130 cStto about 160 cSt at 40° C., and/or about 17 cSt to about 28 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 130 cSt to about 145 cStat 40° C., and/or about 17 cSt to about 23 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 135 cSt to about 140 cSt at 40°C., and/or about 19 cSt to about 21 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40, 42, 44, 46,48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140,150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280,290, 300, 350, or 400 cSt. at 40° C. In some embodiments, the estolidecompounds and compositions may exhibit viscosities of about 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, and 30 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 200, 250, 300, 350, 400, 450, 500, or 550cSt at 0° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 200 cStto about 250 cSt at 0° C. In some embodiments, the estolide compoundsand compositions may exhibit a viscosity within a range from about 250cSt to about 300 cSt at 0° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 300 cSt to about 350 cSt at 0° C. In some embodiments, theestolide compounds and compositions may exhibit a viscosity within arange from about 350 cSt to about 400 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 400 cSt to about 450 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 450 cSt to about 500 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 500 cSt to about 550 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425,450, 475, 500, 525, or 550 cSt at 0° C.

In some embodiments, estolide compounds and compositions may exhibitdesirable low-temperature pour point properties. In some embodiments,the estolide compounds and compositions may exhibit a pour point lowerthan about −25° C., about −35° C., −40° C., or even about −50° C. Insome embodiments, the estolide compounds and compositions have a pourpoint of about −25° C. to about −45° C. In some embodiments, the pourpoint falls within a range of about −30° C. to about −40° C., about −34°C. to about −38° C., about −30° C. to about −45° C., −35° C. to about−45° C., 34° C. to about −42° C., about −38° C. to about −42° C., orabout 36° C. to about −40° C. In some embodiments, the pour point fallswithin the range of about −27° C. to about −37° C., or about −30° C. toabout −34° C. In some embodiments, the pour point falls within the rangeof about −25° C. to about −35° C., or about −28° C. to about −32° C. Insome embodiments, the pour point falls within the range of about −28° C.to about −38° C., or about −31° C. to about −35° C. In some embodiments,the pour point falls within the range of about −31° C. to about −41° C.,or about −34° C. to about −38° C. In some embodiments, the pour pointfalls within the range of about −40° C. to about −50° C., or about −42°C. to about −48° C. In some embodiments, the pour point falls within therange of about −50° C. to about −60° C., or about −52° C. to about −58°C. In some embodiments, the upper bound of the pour point is less thanabout −35° C., about −36° C., about −37° C., about −38° C., about −39°C., about −40° C., about −41° C., about −42° C., about −43° C., about−44° C., or about −45° C. In some embodiments, the lower bound of thepour point is greater than about −70° C., about −69° C., about −68° C.,about −67° C., about −66° C., about −65° C., about −64° C., about −63°C., about −62° C., about −61° C., about −60° C., about −59° C., about−58° C., about −57° C., about −56° C., −55° C., about −54° C., about−53° C., about −52° C., −51, about −50° C., about −49° C., about −48°C., about −47° C., about −46° C., or about −45° C.

In addition, in certain embodiments, the estolides may exhibit decreasedIodine Values (IV) when compared to estolides prepared by other methods.IV is a measure of the degree of total unsaturation of an oil, and isdetermined by measuring the amount of iodine per gram of estolide(cg/g). In certain instances, oils having a higher degree ofunsaturation may be more susceptible to creating corrosiveness anddeposits, and may exhibit lower levels of oxidative stability. Compoundshaving a higher degree of unsaturation will have more points ofunsaturation for iodine to react with, resulting in a higher IV. Thus,in certain embodiments, it may be desirable to reduce the IV ofestolides in an effort to increase the oil's oxidative stability, whilealso decreasing harmful deposits and the corrosiveness of the oil.

In some embodiments, estolide compounds and compositions describedherein have an IV of less than about 40 cg/g or less than about 35 cg/g.In some embodiments, estolides have an IV of less than about 30 cg/g,less than about 25 cg/g, less than about 20 cg/g, less than about 15cg/g, less than about 10 cg/g, or less than about 5 cg/g. The IV of acomposition may be reduced by decreasing the estolide's degree ofunsaturation. This may be accomplished by, for example, by increasingthe amount of saturated capping materials relative to unsaturatedcapping materials when synthesizing the estolides. Alternatively, incertain embodiments, IV may be reduced by hydrogenating estolides havingunsaturated caps.

In certain embodiments, the estolide compounds and compositionsdescribed herein may be used to prepare lubricants and othercompositions. In certain embodiments, the composition comprises at leastone estolide compound selected from Formulas I, II, and III. In certainembodiments, the at least one estolide compound is present in amounts ofabout 0 to about 100 wt. % of the composition, such as about 0.1 toabout 99 wt. %. In certain embodiments, the at least one estolidecompound is present in amounts of about 0 to about 90, about 0 to about80, about 0 to about 70, about 0 to about 60, about 0 to about 50, about0 to about 40, about 0 to about 30, about 0 to about 20, or about 0 toabout 10 wt. % of the composition. In certain embodiments, the at leastone estolide compound is present in amounts of about 25 to about 95 wt.% of the composition, such as about 50 to about 75 wt %. In certainembodiments, the at least one estolide compound is present in amounts ofabout 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 100 wt. %. In certain embodiments, the at least one estolidecompound is present in amounts of about 50, 52, 54, 56, 58, 60, 62, 64,66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, or 98wt. %.

In certain embodiments, the composition comprising the at least oneestolide is a refrigerating fluid. In certain embodiments, therefrigerating fluid further comprises at least one refrigerant. As usedherein, the term “refrigerant” refers to compounds and chemicals thatare suitable for use as heat-transfer fluids in, for example,refrigeration and air conditioning equipment. In certain embodiments,the at least one refrigerant comprises one or more compounds selectedfrom fluorocarbon refrigerants, hydrocarbon refrigerants, carbondioxide, sulfur dioxide, and ammonia. In certain embodiments, the atleast one refrigerant is a fluorocarbon refrigerant comprising one ormore compounds selected from chlorofluorocarbons (CFC),hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC). Incertain embodiments, the at least one refrigerant comprises one or morecompounds selected from fluorine-containing ether refrigerants andnon-fluorine containing ether refrigerants.

In certain embodiments, the at least one refrigerant is an HCFCrefrigerant selected from chlorodifluoromethane (R-22),dichlorofluoromethane (R-21), and bromochlorodifluoromethane (BCF). Incertain embodiments, the HFC refrigerant is selected fromhydrofluorocarbons having 1 to 3 or 1 to 2 carbon atoms. Exemplary HFCsinclude, but are not limited to, difluoromethane (HFC-32),trifluoromethane (HFC-23), pentafluoroethane (HFC-125),1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane(HFC-134a), 1,1,1-trifluoroethane (HFC-143a), and 1,1-difluoroethane(HFC-152a). In certain embodiments, the at least one refrigerant isselected from HFC-32; HFC-23; HFC-134a; HFC-125; a mixture ofHFC-134a/HFC-32, such as 60 to 80% by mass and 40 to 20% by mass,respectively; a mixture of HFC-32/HFC-125, such as 40 to 70% by mass and60 to 30% by mass, respectively; a mixture of HFC-125/HFC-143a, such as40 to 60% by mass and 60 to 40% by mass, respectively; a mixture ofHFC-134a/HFC-32/HFC-125, such as 60% by mass/30% by mass/10% by mass,respectively; a mixture of HFC-134a/HFC-32/HFC-125, such as 40 to 70% bymass/15 to 35% by mass/5 to 40% by mass, respectively; and a mixture ofHFC-125/HFC-134a/HFC-143a, such as 35 to 55% by mass/1 to 15% by mass/40to 60% by mass, respectively. In certain embodiments, the at least onerefrigerant is selected from HFC-134a/HFC-32, such as 70/30% by mass,respectively; a mixture of HFC-32/HFC-125, such as 60/40% by mass,respectively; a mixture of HFC-32/HFC-125, such as 50/50% by mass(R410A); a mixture of HFC-32/HFC-125, such as 45/55% by mass,respectively (R410B); a mixture of HFC-125/HFC-143a, such as 50/50% bymass (R507c); a mixture of HFC-32/1-TFC-125/HFC-134a, such as 10/10/60%by mass, respectively; a mixture of HFC-32/HFC-125/HFC-134a, such as23/25/52% by mass, respectively (R407c); a mixture ofHFC-321HFC-125/HFC-134a, such as 25/15/60% by mass, respectively(R407E); and a mixture of HFC-125/HFC-134a/HFC-143a, such as 44/4/52% bymass, respectively (R404A).

In certain embodiments, the at least one refrigerant is a hydrocarbonrefrigerant. In certain embodiments, the hydrocarbon refrigerant is agas at about 25° C. under 1 atm. In certain embodiments, the hydrocarbonrefrigerant comprises one or more compounds selected from alkanes,cycloalkanes, and alkenes, such as those comprising 1 to 5 carbon atomsor 1 to 4 carbon atoms. In certain embodiments, the hydrocarbonrefrigerant comprises one or more compounds selected from methane,ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane,cyclobutane, and methylcyclopropane.

In certain embodiments, the mass ratio of the at least one estolidecompound to the at least one refrigerant is about 99:1 to about 1:99. Incertain embodiments, the mass ratio of the at least one estolidecompound to the at least one refrigerant is about 95:5, 90:10, 85:15,80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65,30:70, 25:75, 20:80, 15:85, 10:90, or 5:95. In certain embodiments, therefrigerating fluid composition comprises from about 0 wt. % to about 80wt. %, such as about 0 wt. % to about 60 wt. % or about 0 wt. % to about40 wt. % of the at least one estolide compound. In certain embodiments,the at least one estolide compound is present in amounts of about 1 wt.% to about 30 wt. %, about 1 wt. % to about 25 wt. %, or about 5 wt. %to about 20 wt. %. In certain embodiments, the at least one estolidecomprises about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7,7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 wt. % of therefrigerating fluid composition.

In certain embodiments, the refrigerating fluid further comprises atleast one extreme pressure agent. In certain embodiments, the at leastone extreme pressure agent is a phosphorus extreme pressure agent. Incertain embodiments, the phosphorus extreme pressure agent comprises oneor more compounds selected from phosphoric acid esters, acidicphosphoric acid esters, amine salts of phosphoric acid, amine salts ofacidic phosphoric acid esters, amine phosphates, chlorinated phosphoricacid esters, phosphorous acid esters, phosphorylated carboxylic acidcompounds, phosphorothionates, and metal salts of phosphorous-containingcompounds. In certain embodiments, the at least one extreme pressureagent comprises one or more compounds selected from phosphoric acidesters, acidic phosphoric acid esters, amine salts of acidic phosphoricacid esters, chlorinated phosphoric acid esters, and phosphorous acidesters. In certain embodiments, the at least one extreme pressure agentcomprises a phosphorous-containing ester prepared from phosphoric acidand/or phosphorous acid, such as those derived from alkanol orpolyether-type alcohols.

Exemplary phosphoric acid esters include, but are not limited to,tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexylphosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate,tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate,tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate,trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate,trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenylphosphate, cresyldiphenyl phosphate, and xylyldiphenyl phosphate.

Exemplary acidic phosphoric acid esters include, but are not limited to,phosphoric acid monoalkyl esters such as monopropyl acid phosphate,monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acidphosphate, monoheptyl acid phosphate, monooctyl acid phosphate,monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acidphosphate, monododecyl acid phosphate, monotridecyl acid phosphate,monotetradecyl acid phosphate, monopentadecyl acid phosphate,monohexadecyl acid phosphate, monoheptadecyl acid phosphate,monooctadecyl acid phosphate and monooleyl acid phosphate, andphosphoric acid dialkyl esters and phosphoric acid di(alkyl)aryl esterssuch as dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acidphosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acidphosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecylacid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate,dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecylacid phosphate, dioctadecyl acid phosphate and dioleyl acid phosphate.

Exemplary amine salts of acidic phosphoric acid ester include, but arenot limited to, salts of the above-mentioned exemplary acidic phosphoricacid esters with amines such as methylamine, ethylamine, propylamine,butylamine, pentylamine, hexylamine, heptylamine, octylamine,dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine,dihexylamine, diheptylamine, dioctylamine, trimethylamine,triethylamine, tripropylamine, tributylamine, tripentylamine,trihexylamine, triheptylamine, trioctylamine.

Exemplary chlorinated acidic phosphoric acid esters include, but are notlimited to, tris dichloro propyl phosphate, tris chloroethyl phosphate,tris chlorophenyl phosphate, and polyoxyalkylenebis[di(chloroalkyl)]phosphate.

Exemplary phosphorous acid esters include, but are not limited to,dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptylphosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite,diundecyl phosphite, didodecyl phosphite, dioleoyl phosphite, diphenylphosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite,trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonylphosphite, tridecyl phosphite, triundecyl phosphite, tridodecylphosphite, trioleyl phosphite, triphenyl phosphite, and tricresylphosphite.

Exemplary phosphorous-containing carboxylic acids include, but are notlimited to, compounds represented by Formula A:

wherein X is an alkylene residue and R₁, R₂, and R₃ are independentlyselected from hydrogen, optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkylalkyl,optionally substituted aryl, optionally substituted arylalkyl,optionally substituted heteroaryl, optionally substitutedheteroarylalkyl, optionally substituted heterocycloalkyl, and optionallysubstituted heterocycloalkylalkyl.

Exemplary phosphorothionate compounds include, but are not limited to,compounds represented by Formula B:

wherein R₁, R₂, and R₃ are independently selected from hydrogen,optionally substituted alkyl, optionally substituted cycloalkyl,optionally substituted cycloalkylalkyl, optionally substituted aryl,optionally substituted arylalkyl, optionally substituted heteroaryl,optionally substituted heteroarylalkyl, optionally substitutedheterocycloalkyl, and optionally substituted heterocycloalkylalkyl.

Exemplary amine salts of phosphorous-containing compounds include, butare not limited to, alkylamine or alkanolamine salts of phosphoric acid,butylamine phosphates, propanolamine phosphates, and triethanol,monoethanol, dibutyl, dimethyl, and monoisopropanol amine phosphates.

Exemplary metal salts of phosphorous-containing compounds include, butare not limited to, metal salts of the phorphorous compounds describedherein. In certain embodiments, the metal salts of phorphorous compoundsare prepared by neutralizing a part or whole of the acidic hydrogen ofthe phosphorus compound with a metal base. Exemplary metal basesinclude, but are not limited to, metal oxides, metal hydroxides, metalcarbonates, and metal chlorides, wherein said metal is selected fromalkali metals such as lithium, sodium, potassium, and cesium,alkali-earth metals such as calcium, magnesium, and barium, and heavymetals such as zinc, copper, iron, lead, nickel, silver, and manganese.

In certain embodiments, the at least one extreme pressure agent isselected from one or more sulfur compounds. In certain embodiments, theat least one extreme pressure agent comprises one or more compoundsselected from sulfides and polysulfides, such as benzyldisulfide,bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized oils andfats, sulfurized glyceridic oils, sulfurized fatty acids, sulfurizedesters, sulfurized olefins, dihydrocarbyl(poly) sulfides, thiadiazolecompounds, alkylthiocarbamoyl compounds, alkylthiocarbamate compounds,thioterpene compounds, dialkyl thiodipropionate compounds, sulfurizedmineral oils, zinc dithiocarbamate compounds and molybdenumdithiocarbamates, sulfurized alkylphenols, sulfurized dipentenes,sulfurized terpenes, and sulfurized Diels-Alder adducts. Other exemplarysulfur compounds include, but are not limited to, phosphosulfurizedhydrocarbons, such as the reaction product of phosphorus sulfide withturpentine or methyl oleate.

Exemplary dihydrocarbyl(poly)sulfides include, but are not limited to,dibenzyl polysulfides, dinonyl polysulfides, didodecyl polysulfides,dibutyl polysulfides, dioctyl polysulfides, diphenyl polysulfides, anddicyclohexyl polysulfides. Exemplary thiadiazole compounds include, butare not limited to, 1,3,4-thiadiazoles, 1,2,4-thiadiazoles, and1,4,5-thiadiazoles, such as 2,5-bis(n-hexyldithio)-1,3,4-thiadiazole,2,5-bis(n-octyldithio)-1,3,4-thiadiazole,2,5-bis(n-nonyldithio)-1,3,4-thiadiazole,2,5-bis(1,1,3,3-tetramethylbutyldithio)-1,3,4-thiadiazole,3,5-bis(n-hexyldithio)-1,2,4-thiadiazole,3,5-bis(n-octyldithio)-1,2,4-thiadiazole,3,5-bis(n-nonyldithio)-1,2,4-thiadiazole,3,5-bis(1,1,3,3-tetramethylbutyldithio)-1,2,4-thiadiazole,4,5-bis(n-hexyldithio)-1,2,3-thiadiazole,4,5-bis(n-octyldithio)-1,2,3-thiadiazole,4,5-bis(n-nonyldithio)-1,2,3-thiadiazole, and4,5-bis(1,1,3,3-tetramethylbutyldithio)-1,2,3-thiadiazole.

Exemplary alkylthiocarbamoyl compounds include, but are not limited to,bis(dimethylthiocarbamoyl) monosulfide, bis(dibutylthiocarbamoyl)monosulfide, bis(dimethylthiocarbamoyl) disulfide,bis(dibutylthiocarbamoyl) disulfide, bis(diamylthiocarbamoyl) disulfide,and bis(dioctylthiocarbamoyl) disulfide. Exemplary alkylthiocarbamatecompounds include, but are not limited to, methylenebis(dibutyldithiocarbamate) and methylenebis[di(2-ethylhexyl)dithiocarbamate]. Exemplary thioterpene compoundsinclude, but are not limited to, reaction products of phosphoruspentasulfide and pinene. Exemplary dialkyl thiodipropionate compoundsinclude, but are not limited to, dilauryl thiodipropionate and distearylthiodipropionate.

In certain embodiments, the at least one extreme pressure agent ispresent in amounts of about 0 to about 25 wt. % of the refrigeratingfluid composition. In certain embodiments, the at least one extremepressure agent is present in amounts of about 0 to about 20, about 0 toabout 15, about 0 to about 10, about 0 to about 8, about 0 to about 6,about 0 to about 4, or about 0 to about 2 wt. % of the refrigeratingfluid composition. In certain embodiments, the at least one extremepressure agent is present in amounts of about 0 to about 5 wt. % of therefrigerating fluid composition, such as about 0.1 to about 3 wt %. Incertain embodiments, the at least one extreme pressure agent is presentin amounts of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, or 20 wt. %. In certain embodiments, the at least oneextreme pressure agent is present in amounts of about 0.2, 0.4, 0.6,0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 wt. %.

In certain embodiments, the refrigerating composition further comprisesat least one additive selected from separation preventers, stabilityenhancers, biocides, surfactants, corrosion inhibitors, andantioxidants. In certain embodiments, the at least one additive is aseparation preventer comprising one or more compounds selected fromalcohols, amines, ethers, amides, carboxylic acids such as fatty acids,and esters such as alkyl esters of fatty acids. Exemplary alcoholseparation preventers include, but are not limited to, monohydricalcohols and polyhydric alcohols. Exemplary ester separation preventersinclude, but are not limited to, the reaction product of a monohydric orpolyhydric alcohol with a monobasic or polybasic carboxylic acid.Exemplary ether separation preventers include, but are not limited to,the reaction product of the etherification of a monohydric or polyhydricalcohol.

Exemplary monohydric alcohols include, but are not limited to, branchedor unbranched and saturated or unsaturated alcohols. In certainembodiments, the monohydric alcohols may comprise 1 to 24, 1 to 18, 1 to12, or 1 to 8 carbon atoms, such as methanol, ethanol, propanol,butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol,hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol,henicosanol, tricosanol, and tetracosanol.

In certain embodiments, the separation preventer is a polyhydric alcoholcomprising one or more alcohols selected from dihydric to decahydricalcohols, such as dihydric to hexahydric. Exemplary polyhydric alcoholsinclude, but are not limited to, ethylene glycol, diethylene glycol,polyethylene glycols (e.g., trimer to a pentadecamer of ethyleneglycol), propylene glycol, dipropylene glycol, polypropylene glycols(e.g., trimer to a pentadecamer of propylene glycol), 1,3-propanediol,1,2-propanediol, 1,3-butanediol, 1,4-butanediol,2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol,1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol and neopentyl glycol,glycerol, polyglycerols (e.g., dimer to an octamer of glycerol, forexample, diglycerol, triglycerol and tetraglycerol), trimethylolalkanes(e.g., trimethylolethane, tximethylolpropane, trimethylolbutane),pentaerythritols (e.g., dimers to tetramers thereof), 1,2,4-butanetriol,1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol,sorbitan, sorbitol glycerol condensates, adonitol, arabitol, xylitol andmannitol, and saccharides such as xylose, arabinose, ribose, rhamnose,glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose,isomaltose, trehalose and sucrose.

Exemplary carboxylic acid separation preventers include, but are notlimited to, fatty acids, such as saturated or unsaturated and branchedor unbranched fatty acids having 2 to 24, 2 to 18, 2 to 14, 2 to 12, or2 to 8 carbon atoms. In certain embodiments, the carboxylic acidcomprises one or more compounds selected from polybasic acids likedibasic acids, such as acyclic dibasic acids and cyclic dibasic acids.The acyclic dibasic acids may be branched or unbranched and saturated orunsaturated. Exemplary acyclic dibasic acids include, but are notlimited to, those having 2 to 25 carbons, such as ethanedioic acid,propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioicacid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioicacid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid,tetradecanedioic acid, heptadecanedioic acid, hexadecanedioic acid,hexenedioic acid, heptenedioic acid, octenedioic acid, nonenedioic acid,decenedioic acid, undecenedioic acid, dodecenedioic acid, tridecenedioicacid, tetradecenedioic acid, and heptadecenedioic acid. Exemplary cyclicdibasic acids include, but are not limited to,1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid,and aromatic dicarboxylic acids.

Exemplary ether separation preventers include, but are not limited to,triphenyl octyl triether of glycerol, di(methyloxyisopropylene) dodecyltriether of trimethylolpropane, tetrahexyl ether of pentaerythritol,hexapropyl ether of sorbitol, dimethyl dioctyl tetraether of diglycerol,tetra(methyloxyisopropylene) decyl pentaether of triglycerol, hexapropylether of dipentaerythritol, and pentamethyl octyl hexaether oftripentaerythritol.

In certain embodiments, the amine separation preventer comprises one ormore compounds selected from monoamines, polyamines, and alkanol amines,such as alkylamines, alkyl cycloalkyl amines, cycloalkylamines, arylamines, and aromatic-substituted akylamines. Exemplary amines include,but are not limited to, monomethylamine, dimethylamine, trimethylamine,monoethylamine, diethylamine, triethylamine, monopropylamine,dipropylamine, tripropylamine, monobutylamine, dibutylamine,tributylamine, monopentylamine, dipentylamine, tripentylamine,monohexylamine, dihexylamine, monoheptylamine, diheptylamine,monooctylamine, dioctylamine, monononylamine, monodecylamine,monoundecylamine, monododecylamine, monotridecylamine,monotetradecylamine, monopentadecylamine, monohexadecylamine,monoheptadecylamine, monooctadecylamine, monononadecylamine,monoicosylamine, monohenicosylamine, monodocosylamine,monotricosylamine, dimethyl(ethyl)amine, dimethyl(propyl)amine,dimethyl(butyl)amine, dimethyl(pentyl)amine, dimethyl(hexyl)amine,dimethyl(heptyl)amine, dimethyl(octyl)amine, dimethyl(nonyl)amine,dimethyl(decyl)amine, dimethyl(undecyl)amine, dimethyl(dodecyl)amine,dimethyl(tridecyl)amine, dimethyl(tetradecyl)amine,dimethyl(pentadecyl)amine, dimethyl(hexadecyl)amine,dimethyl(heptadecyl)amine, dimethyl(octadecyl)amine,dimethyl(nonadecyl)amine, dimethyl(icosyl)amine,dimethyl(henicosyl)amine, dimethyl(tricosyl)amine; monovinylamine,divinylamine, trivinylamine, monopropenylamine, dipropenylamine,tripropenylamine, monobutenylamine, dibutenylamine, tributenyl amine,monopentenylamine, dipentenyl amine, tripentenylamine, monohexenylamine,dihexenylamine, monoheptenylamine, diheptenylamine, monooctenylamine,dioctenylamine, monononenylamine, monodecenylamine, monoundecenylamine,monododecenylamine, monotridecenylamine, monotetradecenylamine,monopentadecenylamine, monohexadecenylamine, monoheptadecenylamine,monooctadecenylamine, monononadecenylamine, monoicosenylamine,monohenicosenylamine, monodocosenylamine and monotricosenylamine,dimethyl(vinyl)amine, dimethyl(propenyl)amine, dimethyl(butenyl)amine,dimethyl(pentenyl)amine, dimethyl(hexenyl)amine,dimethyl(heptenyl)amine, dimethyl(octenyl)amine, dimethyl(nonenyl)amine,dimethyl(decenyl)amine, dimethyl(undecenyl)amine,dimethyl(dodecenyl)amine, dimethyl(tridecenyl)amine,dimethyl(tetradecenyl)amine, dimethyl(pentadecenyl)amine,dimethyl(hexadecenyl)amine, dimethyl(heptadecenyl)amine,dimethyl(octadecenyl)amine, dimethyl(nonadecenyl)amine,dimethyl(icosenyl)amine, dimethyl(henicosenyl)amine anddimethyl(tricosenyl)amine, monobenzylamine, (1-phenylethyl)amine,(2-phenylethyl)amine (aka: monophenethylamine), dibenzylamine,bis(1-phenylethyl)amine and bis(2-phenylethylene)amine (aka:diphenethylamine), monocyclopentylamine, dicyclopentylamine,tricyclopentylamine, monocyclohexylamine, dicyclohexylamine,monocycloheptylamine, dicycloheptylamine, dimethyl(cyclopentyl)amine,dimethyl(cyclohexyl)amine, dimethyl(cycloheptyl)amine,(methylcyclopentyl)amine, bis(methylcyclopentyl)amine,(dimethylcyclopentyl)amine, bis(dimethylcyclopentyl)amine,(ethylcyclopentyl)amine, bis(ethylcyclopentyl)amine,(methylethylcyclopentyl)amine, bis(methylethylcyclopentyl)amine,(diethylcyclopentyl)amine, (methylcyclohexyl)amine,bis(methylcyclohexyl)amine, (dimethylcyclohexyl)amine,bis(dimethylcyclohexyl)amine, (ethylcyclohexyl)amine,bis(ethylcyclohexyl)amine, (methylethylcyclohexyl)amine,(diethylcyclohexyl)amine, (methylcycloheptyl)amine,bis(methylcycloheptyl)amine, (dimethylcycloheptyl)amine,(ethylcycloheptyl)amine, (methylethylcycloheptyl)amine, and(diethylcycloheptyl)amine. In certain embodiments, the alkanol aminecomprises one or more compounds selected from C₁-C₄ alkanolamines, andprimary, secondary and tertiary alkanol amines. Exemplary alkanol aminesinclude, but are not limited to, mono-, di- and triethanolamine (TEA),and mono-, di- and tri-isopropanolamine.

In certain embodiments, the amide separation preventer comprises atleast one compound derived from the reaction product of a carboxylicacid with a nitrogen-containing compound such as monoamines anddiamines. Suitable carboxylic acids include those previously describedherein, such as fatty acids. Exemplary amide separation inhibitorsinclude, but are not limited to, lauric acid amide, lauric aciddiethanolamide, lauric acid monopropanolamide, myristic acid amide,myristic acid diethanolamide, myristic acid monopropanolamide, palmiticacid amide, palmitic acid diethanolamide, palmitic acidmonopropanolamide, stearic acid amide, stearic acid diethanolamide,stearic acid monopropanolamide, oleic acid amide, oleic aciddiethanolamide, oleic acid monopropanolamide, coconut oil fatty acidamide, coconut oil fatty acid diethanolamide, and coconut oil fatty acidmonopropanolamide.

Exemplary stability enhancers include, but are not limited to, epoxycompounds such as phenylglycidyl ether-type epoxy compounds (e.g.,n-butylphenyl glycidyl ether), alkyl glycidyl ether-type epoxy compounds(e.g., decyl glycidyl ether), glycidyl ester-type epoxy compounds (e.g.,glycidyl-2,2-dimethyl octanoate), allyl oxirane compounds (e.g.,1,2-epoxy styrene), alkyl oxirane compounds (e.g., 1,2-epoxypentane),cycloaliphatic epoxy compounds (e.g., 1,2-epoxycyclopentane), epoxidizedfatty acid monoesters (e.g., hexyl epoxystearate), and epoxidizedvegetable oils.

In certain embodiments, the biocide comprises one or more compoundsselected from antifugal, antimicrobial, and antibacterial agents.Exemplary biocides include, but are not limited to, morpholine-basedcompounds such as 4-(2-nitrobutyl) morpholine,4,4′-(2-ethyl-2-nitrotrimethylene)dimorpholine and methylenedimorpholine, which may be commercially available under the designationsBioban P-1487™, Bioban CS-1135™, and Kaython™ EDC 1.5 (marketed by DowChemical Co.). Other exemplary biocides include, but are not limited to,those comprising the materialpoly(oxy-1,2-ethanediyl(dimethylimino)-1,2-ethanediyl(dimethylimino)-1,2-ethanediyl dichloride, sold under the designationBusan® 77 (marketed by Buckman Laboratories, Inc. of Memphis, Tenn.).

In certain embodiments, the surfactant will aid in the stability andcompatibility of all the ingredients. In certain embodiments, thesurfactant comprises one or more compounds selected from polyols andether and esters thereof, such as glycols, polyglycols, polyalkyleneglycols (PAGs), polyalkylene glycol esters, and copolymers thereof.Exemplary PAGs include, but are not limited to, polyethylene glycols(PEGs) and variants thereof, such as PEG-6 laurate, PEG-8 oleate, PEG-6stearate, PEG-10 stearate, PEG-12 stearate, PEG-8 myristate, PEG-36castor oil, PEG-40 castor oil, PEG-8 tallate, PEG-20 tallate, PEG-14cocoate, PEG-20 sorbitan laurate, PEG-20 sorbitan monopalmitate, PEG-20sorbitan stearate, PEG-20 sorbitan oleate, PEG-20 sorbitan trioleate,PEG-20 sorbitan tristerate, PEG-32, PEG-55, meroxapol 254, poloxamer335, PEG-4, PEG-6, PEG-12, PEG-8 lauryl ether, PEG-10 lauryl ether,PEG-12 cetyl ether, PEG-10 oleyl ether, PEG-10 myristyl ether, PEG-10coconut alcohol PEG-7 nonyl phenyl ether, PEG-10 nonyl phenyl ether,PEG-9 octyl phenyl ether, PEG-16 octyl phenyl ether, and PEG-9 dodecylphenyl ether. Exemplary polyol esters include, but are not limited to,glyceryl esters and sorbitan esters, such as glyceryl monooleate andsorbitan monooleate.

In certain embodiments, the corrosion inhibitor comprises one or morecompounds selected from fatty acids, amines, alkylamines, alkanolamines,alkylamides, alkanolamides, and azole-type compounds such as triazolesand thiazoles. Exemplary corrosion inhibitors include, but are notlimited to, benzothiazoles, benzotriazoles, thiadiazoles, imidazoles,and tolutriazoles, including the sodium salt of mercapto-benzotriazole,naphthotriazole, methylene bis-benzotriazole, dodecyltriazole, andbutylbenzotriazole.

In certain embodiments, the antioxidant comprises one or more compoundsselected from phenolic antioxidants, amine antioxidants, andorganometallic antioxidants. Exemplary amine antioxidants include, butare not limited to, phenyl-α-naphthylamine compounds,dialkyldiphenylamine compounds, benzylamine compounds, and polyaminecompounds. Exemplary phenolic antioxidants include, but are not limitedto, hindered phenolic antioxidants such as 3,5-di-t-butyl 4-hydroxyphenol propionate (e.g., Irganox L135® marketed by Ciba SpecialtyChemicals of Tarrytown, N.Y.) and 2-(4-hydroxy-3,5-di-t-butyl benzylthiol) acetate (e.g., Irganox L118® marketed by Ciba Specialty Chemicalsof Tarrytown, N.Y.). Other exemplary antioxidants include, but are notlimited to, butylated hydroxy toluene (BHT), butylated hydroxy anisole(BHA), and mono-tertiary butyl hydro quinone (TBHQ).

Other optional additives include, but are not limited to, abrasioninhibitors, viscosity index improvers, pour-point depressants,detergent-dispersants, and antifoaming agents.

In certain embodiments, the refrigerating fluid sufficiently satisfiescertain desirable performance characteristics such as lubricity,refrigerant compatibility, low temperature fluidity and stability in agood balance. In certain embodiments, the refrigerating fluid issuitable for refrigerators or heat pumps with a reciprocal or rotaryopen type, semi-hermetic type, or hermetic type compressor. In certainembodiments, when used in a refrigerator with a lead containing bearing,the refrigerating fluid may achieve suppression of elution of the leadfrom the lead-containing bearing, as well as heat/chemical stability. Incertain embodiments, the refrigerating fluid is suitable for use inautomotive air conditioners, dehumidifiers, residential and commercialrefrigeration and air conditioning, freezer/cold storage units andwarehouses, and vending machines. In certain embodiments, therefrigerating fluid is suitable for use in compressors, such asreciprocal compressors, rotary compressors, and centrifugingcompressors.

In certain embodiments, the composition comprising the at least oneestolide compound is a compressor fluid. In certain embodiments, thecompressor fluid is useful as a compressor oil composition forhigh-temperature applications. In certain embodiments, the compressorfluid is suitable for use in rotary gas compressors and gas turbines forelectricity generation. In certain embodiments, the compressor fluidcomprises at least one estolide compound selected from Formulas I, II,and III. In certain embodiments, the compressor fluid further comprisesat least one mist suppressant.

In certain embodiments, the mass ratio of the at least one estolidecompound to the mist suppressant is about 99:1 to about 1:99. In certainembodiments, the mass ratio of the at least one estolide compound to theat least one mist suppressant is about 95:5, 90:10, 85:15, 80:20, 75:25,70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65, 30:70, 25:75,20:80, 15:85, 10:90, or 5:95.

In certain embodiments, the at least one mist suppressant comprises oneor more compounds selected from polymeric materials that include, butare not limited to, polyalkylene oxides (e.g., Polyox® marketed by UnionCarbide), polyolefins, polyacrylates, polymethacrylates,polyacrylamides, polymethacrylamides, polystyrenes, andpolymethylstyrenes, and polymers and copolymers of two or more monomersselected from acrylamides, methyl acrylamides, acrylates, methacrylates,styrenes, methylstyrenes, olefins (e.g., ethylene, propylene,isobutylene), vinyl acetate, and unsaturated organic carboxylic acids(e.g., monounsaturated fatty acids). In certain embodiments, theacrylate and methacrylate monomers are selected from alkyl acrylates,alkylamino acrylates, alkyl methacrylates, and alkylamino methacrylates.In certain embodiments, the polymeric material comprises an averagemolecular weight of about 500-1,000,000 atomic mass units (amu), such asabout 70,000 to about 350,000, or about 100,000 to about 250,000.

In certain embodiments, the desired molecular weight and compatibilityof the at least one mist suppressant is determined by an ability toreduce by 50 wt. % or more of misted (suspended) base oil droplets ascompared to a control of the same oil sheared under the same conditionsin the absence of the polymeric material. In certain embodiments, the atleast one mist suppressant is present in amounts of about 0 to about 30wt. % of the refrigerating fluid composition. In certain embodiments,the at least one mist suppressant is present in amounts of about 0 toabout 20, about 0 to about 15, about 0 to about 10, about 0 to about 8,about 0 to about 6, about 0 to about 4, or about 0 to about 2 wt. % ofthe compressor fluid composition. In certain embodiments, the at leastone mist suppressant is present in amounts of about 0 to about 5 wt. %of the compressor fluid composition, such as about 0.1 to about 3 wt %or 0.01 to about 1 wt. %. In certain embodiments, the at least one mistsuppressant is present in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2,1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 wt. %. In certainembodiments, the at least one mist suppressant is present in amounts ofabout 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1 wt.%.

In certain embodiments, the compressor fluid further comprises at leastone additive comprising one or more compounds selected from separationpreventers, stability enhancers, biocides, surfactants, corrosioninhibitors, and antioxidants, such as those previously described herein.Other optional additives include, but are not limited to, abrasioninhibitors, viscosity index improvers, pour-point depressants,detergent-dispersants, and antifoaming agents.

In certain embodiments, the composition comprising the at least oneestolide compound is a hydraulic fluid. In certain embodiments, thehydraulic fluid may be suitable for use in any of the applications knownto those of skill in the art including, but not limited to, heavymachinery and machine tools, construction equipment, metal-makingequipment, and other industrial processes. In certain embodiments, thehydraulic fluid comprises at least one estolide compound selected fromFormulas I, II, and III. In certain embodiments, the hydraulic fluidfurther comprises at least one extreme pressure agent. In certainembodiments, the at least one extreme pressure agent comprises one ormore compounds selected from phosphorous compounds and sulfur compounds.In certain embodiments, the mass ratio of the at least one estolidecompound to the at least one extreme pressure agent is about 99:1 toabout 1:99. In certain embodiments, the mass ratio of the at least oneestolide compound to the at least one extreme pressure agent is about95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50,45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, or 5:95.

In certain embodiments, the at least one extreme pressure agentcomprises one or more of the phosphorous compounds previously describedherein. In certain embodiments, the at least one extreme pressure agentcomprises one or more of the sulfur compounds previously describedherein.

In certain embodiments, the at least one extreme pressure agent ispresent in amounts of about 0 to about 30 wt. % of the hydraulic fluidcomposition. In certain embodiments, the at least one extreme pressureagent is present in amounts of about 0 to about 20, about 0 to about 15,about 0 to about 10, about 0 to about 8, about 0 to about 6, about 0 toabout 4, or about 0 to about 2 wt. % of the hydraulic fluid composition.In certain embodiments, the at least one extreme pressure agent ispresent in amounts of about 0 to about 5 wt. % of the hydraulic fluidcomposition, such as about 0.1 to about 3 wt % or 0.01 to about 1 wt. %.In certain embodiments, the at least one extreme pressure agent ispresent in amounts of about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8,2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 wt. %. In certain embodiments, the atleast one extreme pressure agent is present in amounts of about 0.01,0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1 wt. %.

In certain embodiments, the hydraulic fluid further comprises at leastone additive selected from one or more of the separation preventers,stability enhancers, biocides, surfactants, corrosion inhibitors, andantioxidants previously described herein. Other optional additivesinclude, but are not limited to, abrasion inhibitors, viscosity indeximprovers, pour-point depressants, detergent-dispersants, andantifoaming agents.

In certain embodiments, the composition comprising the at least oneestolide compound is a metalworking fluid. In certain embodiments, themetalworking fluid may be suitable for use in various metalworkingprocesses including, but not limited to, drawing processes, ironingprocesses, press working processes, forging processes (e.g., hotforging), cutting/grinding processes, and rolling processes (e.g., hotrolling and cold rolling). In certain embodiments, the metalworkingfluids described herein are suitable for the processing of iron,stainless steel, aluminum and alloys thereof, nickel and alloys thereof,chromium and alloys thereof, copper and alloys thereof, zinc and alloysthereof, and titanium and alloys thereof.

In certain embodiments, the metalworking fluid comprises at least oneestolide compound selected from Formulas I, II, and III. In certainembodiments, the metalworking fluid further comprises at least oneextreme pressure agent. In certain embodiments, the mass ratio of the atleast one estolide compound to the at least one extreme pressure agentis about 99:1 to about 1:99. In certain embodiments, the mass ratio ofthe at least one estolide compound to the at least one extreme pressureagent is about 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40,55:45, 50:50, 45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, or5:95.

In certain embodiments, the at least one extreme pressure agent of themetalworking fluid comprises one or more compounds selected from any ofthe extreme pressure agents previously described herein. In certainembodiments, the at least one extreme pressure agent is a phosphorousextreme pressure agent. In certain embodiments, the at least one extremepressure agent comprises one or more compounds selected from amine saltsof phosphoric acid and amine phosphates.

In certain embodiments, the at least one extreme pressure agent ispresent in amounts of about 0 to about 30 wt. % of the metalworkingfluid composition. In certain embodiments, the at least one extremepressure agent is present in amounts of about 0 to about 20, about 0 toabout 15, about 0 to about 10, about 0 to about 8, about 0 to about 6,about 0 to about 4, or about 0 to about 2 wt. % of the metalworkingfluid composition. In certain embodiments, the at least one extremepressure agent is present in amounts of about 0.1 to about 15 wt. % ofthe metalworking fluid composition, such as about 1 to about 10 wt. % or2 to about 8 wt. %. In certain embodiments, the at least one extremepressure agent is present in amounts of about 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 wt. %. In certainembodiments, the at least one extreme pressure agent is present inamounts of about 1, 1.5, 2, 2.5, 2, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5,8, 8.5, 9, 9.5, or 10 wt. %.

In certain embodiments, the metalworking fluid further comprises atleast one surfactant, which may comprise one or more of the surfactantspreviously described herein. In certain embodiments, the metalworkingfluid further comprises at least one biocide, which may comprise one ormore of the biocides previously described herein. In certainembodiments, the metalworking fluid further comprises at least onecorrosion inhibitor, which may comprise one or more of the corrosioninhibitors previously described herein.

In certain embodiments, the metalworking fluid further comprises atleast one additive comprising one or more compound selected fromseparation preventers, stability enhancers, and antioxidants previouslydescribed herein. Other optional additives include, but are not limitedto, abrasion inhibitors, viscosity index improvers, pour-pointdepressants, detergent-dispersants, and antifoaming agents.

In certain embodiments, the metalworking fluid comprises a water-solublecomposition. In certain embodiments, the metalworking fluid comprises anaqueous composition. Accordingly, in certain embodiments, themetalworking fluid further comprises water.

In certain embodiments, the composition comprising the at least oneestolide compound is a food-grade lubricant. In certain embodiments, thefood-grade lubricant is formulated for use in equipment in the foodservice industry, such as general-purpose equipment lubricants, chainlubricants, cable lubricants, spindle lubricants, and gear lubricants.In certain embodiments, the food-grade lubricant comprises at least oneestolide compound selected from Formulas I, II, and III. In certainembodiments, the food-grade lubricant further comprises at least onepolyalphaolefin (PAO). In certain embodiments, the mass ratio of the atleast one estolide compound to the at least one PAO is about 99:1 toabout 1:99. In certain embodiments, the mass ratio of the at least oneestolide compound to the at least one PAO is about 95:5, 90:10, 85:15,80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65,30:70, 25:75, 20:80, 15:85, 10:90, or 5:95.

In certain embodiments, the at least one PAO comprises one or morecompounds selected from PAO2, PAO4, PAO6, PAO8, PAO9, PAO10, PAO40, andPAO100. In certain embodiments, the at least one PAO is present inamounts of about 0 to about 95 wt. % of the food-grade lubricant. Incertain embodiments, the at least one PAO is present in amounts of about0 to about 90, about 0 to about 80, about 0 to about 70, about 0 toabout 60, about 0 to about 50, about 0 to about 40, or about 0 to about30 wt. % of the food-grade lubricant. In certain embodiments, the atleast one PAO is present in amounts of about 30 to about 70 wt. % of thefood-grade lubricant, such as about 40 to about 60 wt % or about 45 toabout 55 wt. %. In certain embodiments, the at least one PAO is presentin amounts of about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, 95 or 100 wt. %. In certain embodiments, the atleast one PAO is present in amounts of about 40, 41, 42, 43, 44, 45, 46,47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,65, 66, 67, 68, 69, or 70 wt. %. In certain embodiments, the food-gradelubricant further comprises at least one antioxidant, which may compriseone or more of the antioxidants previously described herein.

In certain embodiments, the food-grade lubricant further comprises atleast one additive selected from the separation preventers, stabilityenhancers, surfactants, biocides, and corrosion inhibitors previouslydescribed herein. Other optional additives include, but are not limitedto, abrasion inhibitors, viscosity index improvers, pour-pointdepressants, detergent-dispersants, and antifoaming agents.

In certain embodiments, the composition comprising the at least oneestolide compound is a 4-stroke lubricant composition. In certainembodiments, the 4-stroke lubricant composition is suitable for use in4-stroke engines, such as 4-stroke marine engines. Exemplary 4-strokemarine engines include, but are not limited to, slow, fast and semi-fast4-stroke marine engines, such as marine diesel engines. In certainembodiments, the 4-stroke lubricant composition may be used in marinediesel engines as a cylinder lubricant. In certain embodiments, the4-stoke lubricant composition may be used as a lubricant in 4-strokeengines including, but not limited to, outboard and inboard boats andpersonal watercraft, automobiles, motorcycles, dirt bikes and otherall-terrain vehicles.

In certain embodiments, the 4-stroke lubricant composition comprises atleast one estolide compound selected from Formulas I, II, and III. Incertain embodiments, the 4-stroke lubricant composition furthercomprises at least one detergent. Exemplary detergents may include, butare not limited to, metal salts of sulfonic acids, alkylphenols,sulfurized alkylphenols, alkyl salicylates, naphthenates and other oilsoluble mono- and dicarboxylic acid. Neutral or highly basic metal saltssuch as highly basic alkaline earth metal sulfonates (such as calciumand magnesium salts) may be used as such detergents. Nonylphenol sulfidemay also be suitable. Exemplary alkylphenol sulfides may be prepared byreacting an alkylphenol with commercial sulfur dichlorides. Exemplaryalkylphenol sulfides can also be prepared by reacting alkylphenols withelemental sulfur. Other suitable detergents may include, but are notlimited to, neutral and basic salts of phenols, generally known asphenates. In certain embodiments, the phenate comprises an alkylsubstituted phenolic group, wherein the substituent comprises analiphatic hydrocarbon group having about 4 to 400 carbon atoms. Incertain embodiments, the detergent comprises “S911” sold by Infineum USAof Linden, N.J. In some embodiments, the 4-stroke lubricant compositioncomprises from about 0 wt. % to about 25 wt. % of the at least onedetergent, such as about 0 wt. % to about 20 wt. %, about 1 wt. % toabout 15 wt. %, or about 1 wt. % to about 10 wt. %. In certainembodiments, the at least one detergent is present in amounts of about0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9,9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25wt. % of the 4-stroke lubricant composition.

In certain embodiments, the 4-stroke lubricant further comprises atleast one viscosity modifier. In certain embodiments, the at least oneviscosity modifier provides high and low temperature operability to thelubricating oil and permits it to remain shear stable at elevatedtemperatures, while providing acceptable viscosity or fluidity at lowtemperatures. In certain embodiments, the at least one viscositymodifier comprises one or more compounds selected from high molecularweight hydrocarbon polymers, such as polyesters. In certain embodiments,the at least one viscosity modifier is derivatized to include otherproperties or functions, such as the addition of dispersancy properties.Exemplary viscosity modifiers include, but are not limited to,polybutene, polyisobutylene (PIB), copolymers of ethylene and propylene,polymethacrylates, methacrylate copolymers, copolymers of an unsaturateddicarboxylic acid and vinyl compound, interpolymers of styrene andacrylic esters, and partially hydrogenated copolymers ofstyrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well asthe partially hydrogenated homopolymers of butadiene and isoprene.

In certain embodiments, the 4-stroke lubricant comprises at least onepolybutene polymer. In certain embodiments, the at least one polybutenepolymer comprises a mixture of poly-n-butenes and polyisobutylene, whichmay result from the polymerization of C₄ olefins and generally will havea number average molecular weight of about 300 to 1500, or apolyisobutylene or polybutene having a number average molecular weightof about 400 to 1300. In certain embodiments, the polybutene and/orpolyisobutylene may have a number average molecular weight (MW) of about950. MW may be measured by gel permeation chromatography. Polymerscomposed of 100% polyisobutylene or 100% poly-n-butene should beunderstood to fall within the scope of this disclosure and within themeaning of the term “a polybutene polymer”. An exemplary polyisobutyleneincludes “PIB S1054” which has an MW of about 950 and is sold byInfineum USA of Linden, N.J.

In certain embodiments, the at least one polybutene polymer comprises amixture of polybutenes and polyisobutylene prepared from a C₄ olefinrefinery stream containing about 6 wt. % to about 50 wt. % isobutylenewith the balance a mixture of butene (cis- and trans-) isobutylene andless than 1 wt %. butadiene. For example, the at least one polybutenepolymer may be prepared via Lewis acid catalysis from a C₄ streamcomposed of 6-45 wt. % isobutylene, 25-35 wt. % saturated butenes and15-50 wt. % 1- and 2-butenes. In certain embodiments, the 4-strokelubricant composition comprises from about 0 wt. % to about 80 wt. %,such as about 0 wt. % to about 60 wt. % or about 0 wt. % to about 40 wt.% of the at least one polybutene polymer. In certain embodiments, the atleast one polybutene polymer is present in amounts of about 1 wt. % toabout 30 wt. %, about 1 wt. % to about 25 wt. %, or about 5 wt. % toabout 20 wt. %. In certain embodiments, the at least one polybutenepolymer comprises about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6,6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 wt. %of the 4-stroke lubricant composition.

In certain embodiments, the 4-stroke lubricant composition furthercomprises at least one antioxidant. In certain embodiments, the at leastone antioxidant of the 4-stroke lubricant composition comprises one ormore compounds selected from the surfactants previously describedherein. In certain embodiments, the 4-stroke lubricant compositionfurther comprises at least one additive selected from one or more of theseparation preventers, stability enhancers, surfactants, biocides, andcorrosion inhibitors previously described herein. Other optionaladditives include, but are not limited to, abrasion inhibitors,viscosity index improvers, pour-point depressants,detergent-dispersants, and antifoaming agents.

In certain embodiments, the composition comprising the at least oneestolide compound is a plasticized composition. In certain embodiments,the plasticized composition further comprises at least one polymericmaterial. In certain embodiments, the plasticized composition maycomprise a solid, semi-solid, or liquid composition. In certainembodiments, the plasticized composition may be referred to as aplastisol. In certain embodiments, the plastisol comprises a polymericmaterial (e.g., non-crosslinked organic polymer) and a liquid phase(e.g., estolide and/or a diluent).

As used herein, the term “polymeric material” means any synthetic ornaturally-occurring polymeric material, including copolymers andhomopolymers. In certain embodiments, the at least one polymericmaterial comprises one or more compounds selected from polyvinylpolymers, polyolefins, acrylate polymers, methacrylate polymers, styrenepolymers, polyesters, polyamides, polycarbonates, polyurethanes,polysulfides, silicones, elastomers, and rubbers. In certainembodiments, the mass ratio of the at least one estolide compound to theat least one polymeric material is about 99:1 to about 1:99. In certainembodiments, the mass ratio of the at least one estolide compound to theat least one polymeric material is about 95:5, 90:10, 85:15, 80:20,75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65, 30:70,25:75, 20:80, 15:85, 10:90, or 5:95. In certain embodiments, theplasticized composition comprises from about 0 wt. % to about 95 wt. %,such as about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %or about 1 wt. % to about 50 wt. % of the at least one polymericmaterial. In certain embodiments, the at least one polymeric material ispresent in amounts of about 1 wt. % to about 30 wt. %, about 1 wt. % toabout 25 wt. %, or about 0.1 wt. % to about 20 wt. %. In certainembodiments, the at least one polymeric material comprises about 0.5, 1,1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, or 80 wt. % of the plasticized composition.

As used herein, polymeric materials may comprise homopolymers orcopolymers.

Accordingly, unless indicated otherwise, it should be understood thatreference to a polymer such as polyethylene includes, but is not limitedto, a polyethylene homopolymer and a copolymer comprising ethylenemonomers and at least one non-ethylene monomer (e.g., vinyl acetate).Exemplary polymeric materials include, but are not limited to, polyvinylchlorides (PVC), polyethylenes, polypropylenes, polybutylenes,poly(ester amide), polystyrene-polyisobutylene-polystyrene blockcopolymer (SIS), polystyrene, polyisobutylene, polycaprolactone (PCL),poly(L-lactide), poly(D,L-lactide), polylactic acid (PLA),poly(lactide-co-glycolide), poly(glycolide), polyalkylene,polyfluoroalkylene, polyhydroxyalkanoate, poly(3-hydroxybutyrate),poly(4-hydroxybutyrate), poly(3-hydroxyvalerate),poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxyhexanoate),poly(4-hydroxyhexanoate), mid-chain polyhydroxyalkanoate,poly(trimethylene carbonate), poly(orthoester), polyphosphazenes,poly(phosphoester), poly(tyrosine derived arylates), poly(tyrosinederived carbonates), polydimethyloxanone (PDMS), polyvinylidene fluoride(PVDF), polyhexafluoropropylene (HFP), polydimethylsiloxane,poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP),poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE),poly(butyl methacrylate), poly(methyl methacrylate),poly(methacrylates), poly(vinyl acetate), poly(ethylene-co-vinylacetate), poly(ethylene-co-vinyl alcohol), poly(ester urethanes),poly(ether-urethanes), poly(carbonate-urethanes),poly(silicone-urethanes), poly(2-hydroxyethyl methacrylate), Solef™ PVDF(polyvinylidene fluoride), poly(urea-urethanes), hydroxylethylmethacrylate (HEMA), hydroxypropyl methacrylate (HPMA),hydroxypropylmethacrylamide, alkoxymethacrylate, alkoxyacrylate,3-trimethylsilylpropyl methacrylate (TMSPMA), poly(methyl methacrylate)(PMMA), poly(ethylene glycol) (PEG), polypropylene glycol) (PPG), PEGacrylate (PEGA), PEG methacrylate, methacrylic acid (MA), ethylene-vinylacetate, acrylic acid (AA), SIS-PEG, polystyrene-PEG,polyisobutylene-PEG, PCL-PEG, PLA-PEG, PMMA-PEG, PDMS-PEG, PVDF-PEG,poly(tetramethylene glycol), polyhydroxyalkanoates (PHAs), poly(esteramides), polycaprolactones, poly(L-lactide), poly(D,L-lactide),poly(D,L-lactide-co-PEG) block copolymers,poly(D,L-lactide-co-trimethylene carbonate), polyglycolides,poly(lactide-co-glycolide), polydioxanones, polyorthoesters,polyanhydrides, poly(glycolic acid-co-trimethylene carbonate),polyphosphoesters, polyphosphoester urethanes, poly(amino acids),polycyanoacrylates, poly(trimethylene carbonate), poly(imino carbonate),polycarbonates, polyurethanes, copoly(ether-esters) (e.g., PEO/PLA),polyalkylene oxalates, polyphosphazenes, PHA-PEG,poly(alpha-hydroxyacids), poly(beta-hydroxyacids) such aspoly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-valerate)(PHBV), poly(3-hydroxypropionate) (PHP), poly(3-hydroxyhexanoate) (PHH),a poly(4-hydroxyacid) such as poly(4-hydroxybutyrate),poly(4-hydroxyvalerate), or poly(4-hydroxyhexanoate),poly(hydroxyvalerate), polyanhydrides, poly(hydroxyethyl methacylate),poly(N-acylhydroxyproline)esters, poly(N-palmitoylhydroxyproline)esters, polyphosphazenes, poly(tyrosine carbonates), andpoly(tyrosine arylates).

In certain embodiments, the at least one polymeric material isbiodegradable. In certain embodiments, the biodegradable polymericmaterial comprises one or more materials selected from biodegradablepolyesters and biodegradable polyethylenes. Exemplary biodegradablepolyesters include, but are not limited to, polyglycolic acid,polylactic acid, polycaprolactone, polyhydroxybutyrate,polyhydroxyvalerate, and polyhydroxyvaleric acid. Exemplarybiodegradable polyethylenes include, but are not limited to,polyvinylacetate, poly(butylenes succinate), polyvinyl alcohol, andpoly-p-dioxanone.

Exemplary elastomers and rubbers include, but are not limited to,natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR),1,2-butadiene rubber, styrene-butadiene rubber (SBR),acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butylrubber (BR), ethylene-propylene-diene rubber (EPDM) and other dienerubbers and their hydrogenated products, ethylene-propylene rubber(EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM),chlorosulfonated polyethylene, acrylic rubber, fluororubber,polyethylene rubber, polypropylene rubber, and other olefin rubbers,epichlorohydrin rubbers, polysulfide rubbers, silicone rubbers, andurethane rubbers. In certain embodiments, the elastomer may comprise aresin component. Exemplary elastomers may include optionallyhydrogenated polystyrene elastomeric polymers (e.g.,styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), andstyrene-ethylene/butylene-styrene (SEBS)), polyolefin elastomericpolymers, polyvinyl chloride elastomeric polymers, polyurethaneelastomeric polymers, polyester elastomeric polymers, and polyamideelastomeric polymers.

In certain embodiments, the plasticized composition further comprises atleast one thermal stabilizer. In certain embodiments, the at least onethermal stabilizer comprises one or more compounds selected from epoxycompounds, metallic stabilizers, phosphites, nitrogen-containingstabilizers, polyols, hydrotalcites, zeolites, and dawsonites.

Exemplary epoxy thermal stabilizers include, but are not limited to,epoxidized oils such as soybean oil, lard oil, olive oil, linseed oil,peanut oil, castor oil, corn oil, tung oil, and cottonseed oil. Otherexemplary epoxy thermal stabilizers may include, but are not limited to,epichlorhydrin/bis-phenol A resins, butoxypropylene oxide, glycidylepoxystearate, epoxidized alpha-olefins, epoxidized glycidyl soyate,epoxidized butyl toluate, glycidol, vinyl cyclo-hexene dioxide, glycidylethers of resorcinol, hydroquinone, 1,5-dihydroxynaphthalene-,glycerine, pentaerythritol, and sorbitol, allyl glycidyl ether, butylglycidyl ether, cyclohexane oxide, 4-(2,3-epoxyproproxy)acetophenone,mesityl oxide epoxide, and 2-ethyl-3-propyl glycidamine.

Exemplary phosphite thermal stabilizers include, but are not limited to,trialkylphosphites such as trioctyl phosphite, tridecyl phosphite,tridodecyl phosphite, tri(tetradecyl) phosphite, tricyclohexylphosphite, tristearyl phosphite, distearyl-pentaerythritol diphosphite,and trioleyl phosphite; triaryl phosphites such as triphenyl phosphite,tricresyl phosphite, and tris-p-nonylphenyl phosphite, alkyldiarylphosphites such as phenyididecyl phosphite and(2,4-di-tert-butylphenyl)didodecyl phosphite, dialkylaryl phosphites,and thiophosphites such as trithiohexyl phosphite, trithiooctylphosphite, trithiolauryl phosphite, and trithiobenzyl phosphite.

Exemplary metallic thermal stabilizers include, but are not limited to,metal salts and organometallic salts, such as oxides, hydroxides,sulfides, sulfates, halides, phosphates, phenates, perchlorates,carboxylates, and carbonates of metals like zinc, barium, strontium,calcium, tin, magnesium, cobalt, nickel, titanium, antimony, andaluminum, such as calcium hydroxide, magnesium hydroxide, calciumstearate, calcium 2-ethylhexanoate, calcium octanoate, calciumrecinoaleate, calcium myristate, calcium palmitate, barium laurate,barium di(nonylphenolate), barium stearate, aluminum stearate, andhydrotalcite. Exemplary organometallic thermal stabilizers also include,but are not limited to, organotin carboxylates and mercaptides, such asbutyltin tris dodecyl mercaptide, dibutytin dilaurate, dibutyltindidodecyl mercaptide, dianhydride tris dibutylstannane diol,dihydrocarbontin salts of carboxy mercaptals, monosulfides and/orpolysulfides of the organotin mercaptides of mercaptoalkyl carboxylatesand/or alkyl thioglycolates.

Exemplary nitrogen-containing thermal stabilizers include, but are notlimited to, dicyandiamide, hindered amines, melamine, urea, dimethylhydantoin, guanidine, thiourea, 2-phenylindoles, aminocrontonates,N-alkyl and N-phenyl substituted maleimides, 1,3-dialkyl-6-amino-uracilderivatives, pyrrolodiazine diones, and monomeric, oligomeric, andpolymeric 2,2,6,6-tetramethylpiperidine compounds. Other exemplarynonmetallic stabilizers include, but are not limited to,dilaurylthiodipropionate, distearyl 3,3′-thiopropionate,dibenzyl-3,3′-thiodipropionate, dicyclohexyl-3,3′-thiodipropionate,dioleyl-3,3′-thiodipropionate, didecyl-3,3′-thiodipropionate,diethyl-3,3′-thiodipropionate, lauryl ester of 3-mercaptopropionic acid,lauryl ester of 3-lauryl mercaptopropionic acid, and the phenyl ester of3-octyl mercaptopropionic acid.

In addition to the at least one estolide compound, the plasticizedcompositions described herein may further comprise one or moreplasticizers selected from petroleum-derived phthalates and benzoatecompounds, such as dioctyl phthalate (DOP) and diallyl phthalate (DAP).Other exemplary plasticizers include, but are not limited to, one ormore of the exemplary epoxy compound previously described herein.

In certain embodiments, the plasticized composition further comprises atleast one additive comprising one or more compounds selected fromdiluents, pigments, colorants, UV absorbers, fillers, and flameretarding agents. Exemplary diluents include, but are not limited to,hydrocarbons and ketones that are liquids at 25° C. Exemplaryhydrocarbons include aromatic, aliphatic, and/or cycloaliphatichydrocarbons.

In certain embodiments, the plasticized composition may be useful as afilm, coating, ink, or paint composition. In certain embodiments, theplasticized composition comprises a coating that may be applied ontometallic or non-metallic surfaces by dipping, spraying, or the use ofcoating rollers. In certain embodiments, the plasticized compositioncomprises a coating to be applied to fabrics, such as those used in theconstruction of resilient floor and wall coverings.

In certain embodiments, the plasticized composition comprises a solid,semi-solid, and/or molded material. In certain embodiments, theplasticized composition comprises an article of manufacture. In certainembodiments, the article one or more items selected from cookware,storage ware, furniture, appliances, automotive components, boatcomponents, toys, sportswear, medical devices, medical implants,containers, tubes, pipes, sporting equipment, electronics, wirejacketing, cable jacketing, crates, containers, packaging, labware,floor mats, instrumentation, liquid storage containers, bags, pouches,bottles, adhesives, shoe soles, gaskets, elastic fibers, and sealants.In certain embodiments the article is manufactured by any method knownto those of skill in the art. In certain embodiments, the method ofmanufacture is selected from injection molding, compression molding,transfer molding, casting, extruding, thermoforming, blow molding, androtational molding.

It should be understood that in certain embodiments, one or more of thecompositions described herein may be suitable for uses other than thosepreviously set forth herein, such as crankcase oils, gearbox oils,drilling fluids, two-cycle engine oils, greases, heat-treating andcooling compositions, all-purpose and household lubricants, andlubricants for machine tools. In certain embodiments, the nontoxicnature of the estolides described herein may also make them suitable foruse as lubricants in the cosmetic and personal care industry.

In certain embodiments, the estolide compounds may meet or exceed one ormore of the specifications for certain end-use applications, without theneed for conventional additives. For example, in certain instances,high-viscosity lubricants, such as those exhibiting a kinematicviscosity of greater than about 120 cSt at 40° C., or even greater thanabout 200 cSt at 40° C., may be desired for particular applications suchas gearbox or wind turbine lubricants. Prior-known lubricants with suchproperties typically also demonstrate an increase in pour point asviscosity increases, such that prior lubricants may not be suitable forsuch applications in colder environments. However, in certainembodiments, the counterintuitive properties of certain compoundsdescribed herein (e.g., increased EN provides estolides with higherviscosities while retaining, or even decreasing, the oil's pour point)may make higher-viscosity estolides particularly suitable for suchspecialized applications.

Similarly, the use of prior-known lubricants in colder environments maygenerally result in an unwanted increase in a lubricant's viscosity.Thus, depending on the application, it may be desirable to uselower-viscosity oils at lower temperatures. In certain circumstances,low-viscosity oils may include those exhibiting a viscosity of lowerthan about 50 cSt at 40° C., or even about 40 cSt at 40° C. Accordingly,in certain embodiments, the low-viscosity estolides described herein mayprovide end users with a suitable alternative to high-viscositylubricants for operation at lower temperatures.

In some embodiments, it may be desirable to prepare compositionscomprising at least one estolide compound and a non-estolide base oil.For example, in certain embodiments, the estolides described herein maybe co-blended with one or more components selected frompolyalphaolefins, synthetic esters, polyalkylene glycols, and mineraloils (Groups I, II, and III). In addition, or in the alternative, incertain embodiments, the estolides described herein may be co-blendedwith one or more synthetic or petroleum-based oils to achieve desiredviscosity and/or pour point profiles. In certain embodiments, certainestolides described herein also mix well with gasoline, so that they maybe useful as fuel components or additives.

In certain embodiments, the lubricant compositions described hereincomprise a co-blend of at least one estolide base oil or at least oneestolide compound along with at least one further component, wherein theat least one further component is selected from polyalphaolefins,synthetic esters, polyalkylene glycols, mineral oils (Groups I, II, andIII), vegetable and animal-based oils (e.g., mono, di-, andtri-glycerides), and fatty-acid esters. Exemplary mineral oils include,but are not limited to, those available from Petro-Canada under thetrade designation Luminol TR, those available from Calumet LubricatingCo. under the trade designation Caltran 60-15, and those available fromErgon Refining Inc. under the trade designation Hivolt II. Exemplarypolyalphaolefins include, but are not limited to, those having aviscosity from about 2 cSt to about 14 cSt at 100° C., which areavailable from Chevron under the trade designation Synfluid PAO, Amocounder the trade designation Durasyn, and Ethyl Corp. under the tradedesignation Ethylflo. In certain embodiments, the polyalphaolefin has aviscosity from about 4 cSt to about 8 cSt at 100° C., and may originatefrom oligomers such as dimers, trimers, and tetramers. In certainembodiments, the oligomers may comprise chains of 2 to 40 carbons, orchains of 2 to 20 carbons. In certain embodiments, the polyalphaolefinsmay comprise chains of 6 to 12 carbons, such as chains of 10 carbons. Incertain embodiments, the polyalphaolefin has viscosity from about 6 cStto about 8 cSt at 100° C.

The present disclosure further relates to methods of making estolidesaccording to Formula I, II, and III. By way of example, the reaction ofan unsaturated fatty acid with an organic acid and the esterification ofthe resulting free acid estolide are illustrated and discussed in thefollowing Schemes 1 and 2. The particular structural formulas used toillustrate the reactions correspond to those for synthesis of compoundsaccording to Formula I and III; however, the methods apply equally tothe synthesis of compounds according to Formula II, with use ofcompounds having structure corresponding to R₃ and R₄ with a reactivesite of unsaturation.

As illustrated below, compound 100 represents an unsaturated fatty acidthat may serve as the basis for preparing the estolide compoundsdescribed herein.

In Scheme 1, wherein x is, independently for each occurrence, an integerselected from 0 to 20, y is, independently for each occurrence, aninteger selected from 0 to 20, n is an integer greater than or equal to1, and R₁ is an optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched, unsaturated fatty acid 100 maybe combined with compound 102 and a proton from a proton source to formfree acid estolide 104. In certain embodiments, compound 102 is notincluded, and unsaturated fatty acid 100 may be exposed alone to acidicconditions to form free acid estolide 104, wherein R₁ would represent anunsaturated alkyl group. In certain embodiments, if compound 102 isincluded in the reaction, R₁ may represent one or more optionallysubstituted alkyl residues that are saturated or unsaturated andbranched or unbranched. Any suitable proton source may be implemented tocatalyze the formation of free acid estolide 104, including but notlimited to homogenous acids and/or strong acids like hydrochloric acid,sulfuric acid, perchloric acid, nitric acid, triflic acid, and the like.

Similarly, in Scheme 2, wherein x is, independently for each occurrence,an integer selected from 0 to 20, y is, independently for eachoccurrence, an integer selected from 0 to 20, n is an integer greaterthan or equal to 1, and R₁ and R₂ are each an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched, freeacid estolide 104 may be esterified by any suitable procedure known tothose of skilled in the art, such as acid-catalyzed reduction withalcohol 202, to yield esterified estolide 204. Other exemplary methodsmay include other types of Fischer esterification, such as those usingLewis acid catalysts such as BF₃.

In all of the foregoing examples, the compounds described may be usefulalone, as mixtures, or in combination with other compounds,compositions, and/or materials.

Methods for obtaining the novel compounds described herein will beapparent to those of ordinary skill in the art, suitable proceduresbeing described, for example, in the examples below, and in thereferences cited herein.

EXAMPLES

Analytics

Nuclear Magnetic Resonance:

NMR spectra were collected using a Bruker Avance 500 spectrometer withan absolute frequency of 500.113 MHz at 300 K using CDCl₃ as thesolvent. Chemical shifts were reported as parts per million fromtetramethylsilane. The formation of a secondary ester link between fattyacids, indicating the formation of estolide, was verified with 1H NMR bya peak at about 4.84 ppm.

Estolide Number (EN):

The EN was measured by GC analysis. It should be understood that the ENof a composition specifically refers to EN characteristics of anyestolide compounds present in the composition. Accordingly, an estolidecomposition having a particular EN may also comprise other components,such as natural or synthetic additives, other non-estolide base oils,fatty acid esters, e.g., triglycerides, and/or fatty acids, but the ENas used herein, unless otherwise indicated, refers to the value for theestolide fraction of the estolide composition.

Iodine Value (IV):

The iodine value is a measure of the degree of total unsaturation of anoil. IV is expressed in terms of centigrams of iodine absorbed per gramof oil sample. Therefore, the higher the iodine value of an oil thehigher the level of unsaturation is of that oil. The IV may be measuredand/or estimated by GC analysis. Where a composition includesunsaturated compounds other than estolides as set forth in Formula I,II, and III, the estolides can be separated from other unsaturatedcompounds present in the composition prior to measuring the iodine valueof the constituent estolides. For example, if a composition includesunsaturated fatty acids or triglycerides comprising unsaturated fattyacids, these can be separated from the estolides present in thecomposition prior to measuring the iodine value for the one or moreestolides.

Acid Value:

The acid value is a measure of the total acid present in an oil. Acidvalue may be determined by any suitable titration method known to thoseof ordinary skill in the art. For example, acid values may be determinedby the amount of KOH that is required to neutralize a given sample ofoil, and thus may be expressed in terms of mg KOH/g of oil.

Gas Chromatography (GC):

GC analysis was performed to evaluate the estolide number (EN) andiodine value (IV) of the estolides. This analysis was performed using anAgilent 6890N series gas chromatograph equipped with a flame-ionizationdetector and an autosampler/injector along with an SP-2380 30 m×0.25 mmi.d. column.

The parameters of the analysis were as follows: column flow at 1.0mL/min with a helium head pressure of 14.99 psi; split ratio of 50:1;programmed ramp of 120-135° C. at 20° C./min, 135-265° C. at 7° C./min,hold for 5 min at 265° C.; injector and detector temperatures set at250° C.

Measuring EN and IV by GC:

To perform these analyses, the fatty acid components of an estolidesample were reacted with MeOH to form fatty acid methyl esters by amethod that left behind a hydroxy group at sites where estolide linkswere once present. Standards of fatty acid methyl esters were firstanalyzed to establish elution times.

Sample Preparation:

To prepare the samples, 10 mg of estolide was combined with 0.5 mL of0.5M KOH/MeOH in a vial and heated at 100° C. for 1 hour. This wasfollowed by the addition of 1.5 mL of 1.0 M H₂SO₄/MeOH and heated at100° C. for 15 minutes and then allowed to cool to room temperature. One(1) mL of H₂O and 1 mL of hexane were then added to the vial and theresulting liquid phases were mixed thoroughly. The layers were thenallowed to phase separate for 1 minute. The bottom H₂O layer was removedand discarded. A small amount of drying agent (Na₂SO₄ anhydrous) wasthen added to the organic layer after which the organic layer was thentransferred to a 2 mL crimp cap vial and analyzed.

EN Calculation:

The EN is measured as the percent hydroxy fatty acids divided by thepercent non-hydroxy fatty acids. As an example, a dimer estolide wouldresult in half of the fatty acids containing a hydroxy functional group,with the other half lacking a hydroxyl functional group. Therefore, theEN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fattyacids, resulting in an EN value of 1 that corresponds to the singleestolide link between the capping fatty acid and base fatty acid of thedimer.

IV Calculation:

The iodine value is estimated by the following equation based on ASTMMethod D97 (ASTM International, Conshohocken, Pa.):

${I\; V} = {\sum{100 \times \frac{A_{f} \times {MW}_{I} \times {db}}{{MW}_{f}}}}$

-   -   A_(f)=fraction of fatty compound in the sample    -   MW_(I)=253.81, atomic weight of two iodine atoms added to a        double bond    -   db=number of double bonds on the fatty compound    -   MW_(f)=molecular weight of the fatty compound

The properties of exemplary estolide compounds and compositionsdescribed herein are identified in the following examples and tables.

Other Measurements:

Except as otherwise described, color is measured by ASTM Method D1500,neutralization number (TAN) is measured by ASTM Method D974, pour pointis measured by ASTM Method D97-96a, cloud point is measured by ASTMMethod D2500, viscosity/kinematic viscosity is measured by ASTM MethodD445-97, viscosity index is measured by ASTM Method D2270-93 (Reapproved1998), specific gravity is measured by ASTM Method D4052, fire point andflash point are measured by ASTM Method D92, evaporative loss ismeasured by ASTM Method D5800, vapor pressure is measured by ASTM MethodD5191, and acute aqueous toxicity is measured by Organization ofEconomic Cooperation and Development (OECD) 203.

Example 1

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (65 Kg, OL 700, Twin Rivers)was added to the reactor with 70% perchloric acid (992.3 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs (Torr absolute; 1torr=˜1 mmHg)) for 24 hrs while continuously being agitated. After 24hours the vacuum was released. 2-Ethylhexanol (29.97 Kg) was then addedto the reactor and the vacuum was restored. The reaction was allowed tocontinue under the same conditions (60° C., 10 torr abs) for 4 morehours. At which time, KOH (645.58 g) was dissolved in 90% ethanol/water(5000 mL, 90% EtOH by volume) and added to the reactor to quench theacid. The solution was then allowed to cool for approximately 30minutes. The contents of the reactor were then pumped through a 1 micron(t) filter into an accumulator to filter out the salts. Water was thenadded to the accumulator to wash the oil. The two liquid phases werethoroughly mixed together for approximately 1 hour. The solution wasthen allowed to phase separate for approximately 30 minutes. The waterlayer was drained and disposed of. The organic layer was again pumpedthrough a 1μ filter back into the reactor. The reactor was heated to 60°C. in vacuo (10 torr abs) until all ethanol and water ceased to distillfrom solution. The reactor was then heated to 100° C. in vacuo (10 torrabs) and that temperature was maintained until the 2-ethylhexanol ceasedto distill from solution. The remaining material was then distilledusing a Myers 15 Centrifugal Distillation still at 200° C. under anabsolute pressure of approximately 12 microns (0.012 torr) to remove allmonoester material leaving behind estolides (Ex. 1). Certain data arereported below in Tables 1 and 8.

Example 2

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (50 Kg, OL 700, Twin Rivers)and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) wereadded to the reactor with 70% perchloric acid (1145 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (34.58 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(744.9 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1 t filter into an accumulator tofilter out the salts. Water was then added to the accumulator to washthe oil. The two liquid phases were thoroughly mixed together forapproximately 1 hour. The solution was then allowed to phase separatefor approximately 30 minutes. The water layer was drained and disposedof. The organic layer was again pumped through a 1 t filter back intothe reactor. The reactor was heated to 60° C. in vacuo (10 torr abs)until all ethanol and water ceased to distill from solution. The reactorwas then heated to 100° C. in vacuo (10 torr abs) and that temperaturewas maintained until the 2-ethylhexanol ceased to distill from solution.The remaining material was then distilled using a Myers 15 CentrifugalDistillation still at 200° C. under an absolute pressure ofapproximately 12 microns (0.012 torr) to remove all monoester materialleaving behind estolides (Ex. 2). Certain data are reported below inTables 2 and 7.

Example 3

The estolides produced in Example 1 (Ex. 1) were subjected todistillation conditions in a Myers 15 Centrifugal Distillation still at300° C. under an absolute pressure of approximately 12 microns (0.012torr). This resulted in a primary distillate having a lower EN average(Ex. 3A), and a distillation residue having a higher EN average (Ex.3B). Certain data are reported below in Tables 1 and 8.

TABLE 1 Pour Iodine Estolide Point Value Base Stock EN (° C.) (cg/g) Ex.3A 1.35 −32 31.5 Ex. 1 2.34 −40 22.4 Ex. 3B 4.43 −40 13.8

Example 4

Estolides produced in Example 2 (Ex. 2) were subjected to distillationconditions in a Myers 15 Centrifugal Distillation still at 300° C. underan absolute pressure of approximately 12 microns (0.012 torr). Thisresulted in a primary distillate having a lower EN average (Ex. 4A), anda distillation residue having a higher EN average (Ex. 4B). Certain dataare reported below in Tables 2 and 7.

TABLE 2 Estolide Iodine Base Stock EN Pour Point (° C.) Value (cg/g) Ex.4A 1.31 −30 13.8 Ex. 2 1.82 −33 13.2 Ex. 4B 3.22 −36 9.0

Example 5

Estolides produced by the method set forth in Example 1 were subjectedto distillation conditions (ASTM D-6352) at 1 atm (atmosphere) over thetemperature range of about 0° C. to about 710° C., resulting in 10different estolide cuts recovered at increasing temperatures The amountof material distilled from the sample in each cut and the temperature atwhich each cut distilled (and recovered) are reported below in Table 3:

TABLE 3 Cut (% of total) Temp. (° C.) 1 (1%) 416.4 2 (1%) 418.1 3 (3%)420.7  4 (20%) 536.4  5 (25%) 553.6  6 (25%) 618.6  7 (20%) 665.7 8 (3%)687.6 9 (1%) 700.6 10 (1%)  709.1

Example 6

Estolides made according to the method of Example 2 were subjected todistillation conditions (ASTM D-6352) at 1 atm over the temperaturerange of about 0° C. to about 730° C., which resulted in 10 differentestolide cuts. The amount of each cut and the temperature at which eachcut was recovered are reported in Table 4.

TABLE 4 Cut (% of total) Temp. (° C.) 1 (1%) 417.7 2 (1%) 420.2 3 (3%)472.0 4 (5%) 509.7  5 (15%) 533.7  6 (25%) 583.4  7 (25%) 636.4 8 (5%)655.4 9 (5%) 727.0 10 (15%) >727.0

Example 7

Estolide base oil 4B (from Example 4) was subjected to distillationconditions (ASTM D-6352) at 1 atm over the temperature range of about 0°C. to about 730° C., which resulted in 9 different estolide cuts. Theamount of each cut and the temperature at which each cut was recoveredare reported in Table 5a.

TABLE 5a Cut (% of total) Temp. (° C.) 1 (1%) 432.3 2 (1%) 444.0 3 (3%)469.6 4 (5%) 521.4  5 (15%) 585.4  6 (25%) 617.1  7 (25%) 675.1 8 (5%)729.9  9 (20%) >729.9

Example 8

Estolides were made according to the method set forth in Example 1,except that the 2-ethylhexanol esterifying alcohol used in Example 1 wasreplaced with various other alcohols. Alcohols used for esterifictaioninclude those identified in Table 5b below. The properties of theresulting estolides are set forth in Table 9.

TABLE 5b Alcohol Structure Jarcol ™ I-18CG iso-octadecanol Jarcol ™ I-122-butyloctanol Jarcol ™ I-20 2-octyldodecanol Jarcol ™ I-162-hexyldecanol Jarcol ™ 85BJ cis-9-octadecen-1-ol Fineoxoco ® 180

Jarcol ™ I-18T 2-octyldecanol

Example 9

Estolides were made according to the method set forth in Example 2,except the 2-ethylhexanol esterifying alcohol was replaced withisobutanol. The properties of the resulting estolides are set forth inTable 9.

Example 10

Estolides of Formula I, II, and III are prepared according to the methodset forth in Examples 1 and 2, except that the 2-ethylhexanolesterifying alcohol is replaced with various other alcohols. Alcohols tobe used for esterifictaion include those identified in Table 6 below.Esterifying alcohols to be used, including those listed below, may besaturated or unsaturated, and branched or unbranched, or substitutedwith one or more alkyl groups selected from methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, hexyl, isohexyl, and the like, to form a branched orunbranched residue at the R₂ position. Examples of combinations ofesterifying alcohols and R₂ Substituents are set forth below in Table 6:

TABLE 6 Alcohol R₂ Substituents C₁ alkanol methyl C₂ alkanol ethyl C₃alkanol n-propyl, isopropyl C₄ alkanol n-butyl, isobutyl, sec-butyl C₅alkanol n-pentyl, isopentyl neopentyl C₆ alkanol n-hexyl, 2-methylpentyl, 3- methyl pentyl, 2,2-dimethyl butyl, 2,3-dimethyl butyl C₇alkanol n-heptyl and other structural isomers C₈ alkanol n-octyl andother structural isomers C₉ alkanol n-nonyl and other structural isomersC₁₀ alkanol n-decanyl and other structural isomers C₁₁ alkanoln-undecanyl and other structural isomers C₁₂ alkanol n-dodecanyl andother structural isomers C₁₃ alkanol n-tridecanyl and other structuralisomers C₁₄ alkanol n-tetradecanyl and other structural isomers C₁₅alkanol n-pentadecanyl and other structural isomers C₁₆ alkanoln-hexadecanyl and other structural isomers C₁₇ alkanol n-heptadecanyland other structural isomers C₁₈ alkanol n-octadecanyl and otherstructural isomers C₁₉ alkanol n-nonadecanyl and other structuralisomers C₂₀ alkanol n-icosanyl and other structural isomers C₂₁ alkanoln-heneicosanyl and other structural isomers C₂₂ alkanol n-docosanyl andother structural isomers

TABLE 7 ASTM PROPERTY ADDITIVES METHOD Ex. 4A Ex. 2 Ex. 4B Color None —Light Amber Amber Gold Specific Gravity None D 4052 0.897 0.904 0.912(15.5° C.), g/ml Viscosity - None D 445 32.5 65.4 137.3 Kinematic at 40°C., cSt Viscosity - None D 445 6.8 11.3 19.9 Kinematic at 100° C., cStViscosity Index None D 2270 175 167 167 Pour Point, ° C. None D 97 −30−33 −36 Cloud Point, ° C. None D 2500 −30 −32 −36 Flash Point, ° C. NoneD 92 278 264 284 Fire Point, ° C. None D 92 300 300 320 Evaporative LossNone D 5800 1.9 1.4 0.32 (NOACK), wt. % Vapor Pressure - None D 5191 ≈0≈0 ≈0 Reid (RVP), psi

TABLE 8 ASTM PROPERTY ADDITIVES METHOD Ex. 3A Ex. 1 Ex. 3B Color None —Light Amber Amber Gold Specific Gravity None D 4052 0.897 0.906 0.917(15.5° C.), g/ml Viscosity - None D 445 40.9 91.2 211.6 Kinematic at 40°C., cSt Viscosity - None D 445 8.0 14.8 27.8 Kinematic at 100° C., cStViscosity Index None D 2270 172 170 169 Pour Point, ° C. None D 97 −32−40 −40 Cloud Point, ° C. None D 2500 −32 −33 −40 Flash Point, ° C. NoneD 92 278 286 306 Fire Point, ° C. None D 92 300 302 316 Evaporative LossNone D 5800 1.4 0.8 0.3 (NOACK), wt. % Vapor Pressure - None D 5191 ≈0≈0 ≈0 Reid (RVP), psi

TABLE 9 Estimated Pour Cloud Example EN Pt. Pt. Visc. @ Visc. @ Visc. #Alcohol (approx.) ° C. ° C. 40° C. 100° C. Index 8 Jarcol ™ I-18CG2.0-2.6 −15 −13 103.4 16.6 174 8 Jarcol ™ I-12 2.0-2.6 −39 −40 110.916.9 166 8 Jarcol ™ I-20 2.0-2.6 −42 <−42 125.2 18.5 166 8 Jarcol ™ I-162.0-2.6 −51 <−51 79.7 13.2 168 8 Jarcol ™ 85BJ 2.0-2.6 −15 −6 123.8 19.5179 8 Fineoxocol ® 180 2.0-2.6 −39 −41 174.2 21.1 143 8 Jarcol ™ I-18T2.0-2.6 −42 <−42 130.8 19.2 167 8 Isobutanol 2.0-2.6 −36 −36 74.1 12.6170 9 Isobutanol 1.5-2.2 −36 −36 59.5 10.6 170

Example 11

Saturated and unsaturated estolides having varying acid values weresubjected to several corrosion and deposit tests. These tests includedthe High Temperature Corrosion Bench Test (HTCBT) for several metals,the ASTM D130 corrosion test, and the MHT-4 TEOST (ASTM D7097) test forcorrelating piston deposits. The estolides tested having higher acidvalues (0.67 mg KOH/g) were produced using the method set forth inExamples 1 and 4 for producing Ex. 1 and Ex. 4A (Ex.1* and Ex.4A*below). The estolides tested having lower acid values (0.08 mg KOH/g)were produced using the method set forth in Examples 1 and 4 forproducing Ex. 1 and Ex. 4A except the crude free-acid estolide wasworked up and purified prior to esterification with BF₃.OET₂ (0.15equiv.; reacted with estolide and 2-EH in Dean Stark trap at 80° C. invacuo (10 torr abs) for 12 hrs while continuously being agitated; crudereaction product washed 4×H₂O; excess 2-EH removed by heating washedreaction product to 140° C. in vacuo (10 torr abs) for 1 hr) (Ex.4A#below). Estolides having an IV of 0 were hydrogenated via 10 wt. %palladium embedded on carbon at 75° C. for 3 hours under a pressurizedhydrogen atmosphere (200 psig) (Ex.4A*H and Ex.4A#H below) The corrosionand deposit tests were performed with a Dexos™ additive package. Resultswere compared against a mineral oil standard:

TABLE 10 Ex. 1* Ex. 4A* Ex. 4A*H Ex. 4A# Ex. 4A#H Standard EstolideEstolide Estolide Estolide Estolide Acid Value — ~0.7 0.67 0.67 0.080.08 (mg KOH/g) Iodine Value (IV) — ~45 16 0 16 0 HTCBT Cu 13 739 279 609.3 13.6 HTCBT Pd 177 11,639 1,115 804 493 243 HTCBT Sn 0 0 0 0 0 0 ASTMD130 1A 4B 3A 1B 1A 1A MHT-4 18 61 70 48 12 9.3

Example 12

“Ready” and “ultimate” biodegradability of the estolide produced in Ex.1 was tested according to standard OECD procedures. Results of the OECDbiodegradability studies are set forth below in Table 11:

TABLE 11 301D 28-Day 302D Assay (% degraded) (% degraded) Canola Oil86.9 78.9 Ex. 1 64.0 70.9 Base Stock

Example 13

The Ex. 1 estolide base stock from Example 1 was tested under OECD 203for Acute Aquatic Toxicity. The tests showed that the estolides arenontoxic, as no deaths were reported for concentration ranges of 5,000mg/L and 50,000 mg/L.

Example 14

The miscibility of the Ex. 4A estolide base stock in certainrefrigerants was tested at different weight percentages of the overallestolide/refrigerant composition, as well as the low temperature down towhich miscibility was achieved. The results of the miscible(M)-immiscible (I) study are set forth below in Table 12:

TABLE 12 Wt. % of Ex. 4A estolide Low Temp. Refrigerant 2% 5% 10% 20%30% (° C.) HFC-134a I I I I I — R-22 NT* M M M M −40 R-404A I I I I I —R-407C I I I I I — R-410A I I I I I — *NT = Not Tested

Example 15

Refrigerating fluid compositions are prepared in the manner set forth inExample 14, except the Ex. 4A estolide base stock is replaced withestolides prepared according to the method set forth in Ex. 1, Ex. 2,Ex. 3 (3A and 3B), and Ex. 4B to provide separate refrigerating fluidcompositions for each estolide.

The invention claimed is:
 1. A composition consisting essentially of twoor more saturated estolide compounds, said composition having: an ENthat is greater than 1.0 and less than 1.4, wherein the EN is theaverage number of estolide linkages in estolide compounds of thecomposition; and a kinematic viscosity of about 3 cSt, about 4 cSt,about 5 cSt, about 6 cSt, or about 7 cSt, each when measured at 100° C.2. The composition of claim 1, wherein the two or more saturatedestolide compounds are selected from compounds of Formula I:

wherein x is, independently for each occurrence, an integer selectedfrom 0 to 10; y is, independently for each occurrence, an integerselected from 0 to 10; n is an integer selected from 0 to 4; R₁ is anunsubstituted C₁ to C₁₈ alkyl that is saturated, and branched orunbranched; and R₂ is an unsubstituted C₁ to C₁₈ alkyl that issaturated, and branched or unbranched, wherein each fatty acid chainresidue of said at least one compound is unsubstituted.
 3. Thecomposition of claim 2, wherein R₁ is selected from C₁ alkyl, C₃ alkyl,C₅ alkyl, C₇ alkyl, C₉ alkyl, C₁₀ alkyl, and C₁₁ alkyl.
 4. Thecomposition of claim 2, wherein R₁ is unbranched.
 5. The composition ofclaim 2, wherein R₂ is branched.
 6. The composition of claim 5, whereinR₂ is a C₆ to C₁₂ alkyl.
 7. The composition of claim 6, wherein R₂ is2-ethylhexyl.
 8. The composition of claim 2, wherein x is, independentlyfor each occurrence, selected from 7, 8, 9, and
 10. 9. The compositionof claim 8, wherein y is, independently for each occurrence, selectedfrom 5, 6, 7, and
 8. 10. The composition of claim 2, wherein x is 1 foreach occurrence.
 11. The composition of claim 10, wherein y is 10 foreach occurrence.
 12. The composition of claim 2, wherein x is,independently for each occurrence, selected from 3, 4, 5, or
 6. 13. Thecomposition of claim 12, wherein y is, independently for eachoccurrence, selected from 6, 7, 8, and
 9. 14. The composition of claim2, wherein R₁ is methyl.
 15. The composition of claim 14, wherein R₂ isbranched.
 16. The composition of claim 15, wherein R₂ is a C₆ to C₁₂alkyl.
 17. The composition of claim 16, wherein R₂ is 2-ethylhexyl. 18.A composition containing saturated estolide compounds, said compositioncomprising at least one saturated dimer estolide compound, wherein thecomposition has an EN that is greater than 1.0 and less than 1.4,wherein the EN is the average number of estolide linkages in estolidecompounds of the composition, and wherein the composition has akinematic viscosity of about 3 cSt, about 4 cSt, about 5 cSt, about 6cSt, or about 7 cSt, each when measured at 100° C.
 19. The compositionof claim 18, further comprising at least one additive.
 20. Thecomposition of claim 19, wherein the at least one additive is selectedfrom one or more of a separation preventer, a stability enhancer, abiocide, a surfactant, a corrosion inhibitor, an antioxidant, anabrasion inhibitor, a viscosity index improver, a pour-point depressant,a detergent-dispersant, and an antifoaming agent.
 21. The composition ofclaim 18, further comprising at least one amine antioxidant.
 22. Acomposition comprising an estolide base oil, said estolide base oilhaving a kinematic viscosity of about 3 cSt, about 4 cSt, about 5 cSt,about 6 cSt, or about 7 cSt, each when measured at 100° C., wherein theestolide base oil comprises two or more saturated estolide compoundsselected from Formula II:

wherein m is an integer greater than or equal to 1; n is 0 to 10; R₁,independently for each occurrence, is an optionally substituted alkylthat is saturated, and branched or unbranched; R₂ is selected fromoptionally substituted alkyl that is saturated and branched orunbranched; and R₃ and R₄, independently for each occurrence, areselected from optionally substituted alkyl that is saturated, andbranched or unbranched; wherein each fatty acid chain residue of saidestolide compounds is unsubstituted, and wherein n=1 for at least one ofthe estolide compounds comprising the estolide base oil.
 23. Thecomposition of claim 22, wherein the composition consists essentially ofthe two or more estolide compounds.
 24. The composition of claim 23,wherein m=1.
 25. The composition of claim 24, wherein n=0 for at leastone of the estolide compounds.
 26. The composition of claim 25, whereinR₁ is an unsubstituted C₁ to C₁₈ alkyl that is saturated, and branchedor unbranched, and wherein R₂ is an unsubstituted C₁ to C₁₈ alkyl thatis saturated and branched or unbranched.
 27. The composition of claim26, wherein R₃ and R₄ are, independently for each occurrence, selectedfrom C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl,each of which is saturated, and branched or unbranched.
 28. Thecomposition of claim 3, wherein the composition has a kinematicviscosity of about 3 cSt or about 4 cSt.
 29. The composition of claim 3,wherein the composition has a kinematic viscosity of about 6 cSt. 30.The composition of claim 18, wherein the composition has a kinematicviscosity of about 3 cSt or about 4 cSt.
 31. The composition of claim18, wherein the composition has a kinematic viscosity of about 6 cSt.32. The composition of claim 23, wherein the composition has a kinematicviscosity of about 3 cSt or about 4 cSt.
 33. The composition of claim23, wherein the composition has a kinematic viscosity of about 6 cSt.